Macrocyclic picolinamides as fungicides

ABSTRACT

The disclosure relates to macrocyclic picolinamides of Formula (I) and to the use of these compounds as fungicides.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/747,723 filed Dec. 31, 2012, which is expressly incorporated by reference herein.

BACKGROUND AND SUMMARY

Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.

The present disclosure relates to macrocyclic picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

One embodiment of the present disclosure may include compounds of Formula I:

X is H or C(O)R₅;

Y is H, C(O)R₅, or Q;

Q is

R₁ is H, alkyl, alkenyl, aryl, —C(O)R₄, each substituted with 0, 1 or multiple R₄;

R₂ is H, alkyl, alkenyl, aryl, —C(O)R₄, each substituted with 0, 1 or multiple R₄;

R₃ is H, —C(O)R₆ or —CH₂OC(O)R₆;

R₄ is alkyl, alkenyl, halo, haloalkyl, alkoxy, or aryl;

R₅ is alkyl, alkoxy, benzyl, benzyloxy, each substituted with 0, 1, or multiple R₇, wherein each R₇ may be substituted with 0, 1, or multiple R₄;

R₆ is alkyl or alkoxy, each substituted with 0, 1, or multiple R⁴;

R₇ is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl, carbocyclic, heterocyclic, —Si(R₄)₃, —C(O)R₄, —S(O)_(n)R₄, each substituted with 0, 1, or multiple R₄;

and with the proviso that when R₁ and R₂ are H then X and Y are C(O)R₅ and R₅ is tert-butoxy.

Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.

Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, an area adjacent to the plant, and the seed adapted to produce the plant.

The term “alkyl” refers to a branched or unbranched carbon chain, including methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The term “alkenyl” refers to a branched or unbranched carbon chain containing one or more double bonds including ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclopentenyl, cyclohexenyl, and the like.

The term “alkynyl” refers to a branched or unbranched carbon chain containing one or more triple bonds including propynyl, butyryl and the like.

The term “aryl” refers to any aromatic, mono- or bi-cyclic, containing 0 heteroatoms.

The term “heterocyclyl” refers to any aromatic or non-aromatic ring, mono- or bi-cyclic, containing one or more heteroatoms

The term “cycloalkyl” refers to any monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.

The term “cycloalkenyl” refers to any monocyclic or polycyclic, unsaturated (at least one carbon-carbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.

The term “alkoxy” refers to an —OR substituent.

The term “alkoxycarbonyl” refers to a —C(O)—OR substituent.

The term “alkylcarbonyl” refers to a —C(O)—R substituent.

The term “alkylsulfonyl” refers to an —SO₂—R substituent.

The term “haloalkylsulfonyl” refers to an —SO₂—R substituent where R is fully or partially substituted with Cl, F, I, or Br or any combination thereof.

The term “alkylthio” refers to an —S—R substituent.

The term “haloalkylthio” refers to an alkylthio, which is substituted with Cl, F, I, or Br or any combination thereof.

The term “alkylaminocarbonyl” refers to a —C(O)—N(H)—R substituent.

The term “dialkylaminocarbonyl” refers to a —C(O)—NR₂ substituent.

The term “alkylcycloalkylamino” refers to a cycloalkylamino substituent that is substituted with an alkyl group.

The term “trialkylsilyl” refers to —SiR₃.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to an —OH substituent.

The term “amino” refers to a —NH₂ substituent.

The term “alkylamino” refers to a —N(H)—R substituent.

The term “dialkylamino” refers to a —NR₂ substituent.

The term “alkoxyalkoxy” refers to —O(CH₂)_(n)O(CH₂)_(n) where n is an integer selected from the list 1, 2, 3, 4, 5, or 6.

The term “alkoxyalkyl” refers to an alkoxy substitution on an alkyl.

The term “haloalkoxyalkyl” refers to an alkoxy substitution on an alkyl which may be partially substituted with halogen atoms.

The term “hydroxyalkyl” refers to an alkyl which is substituted with a hydroxyl group.

The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl, F, Br, or I, or any combination thereof.

The term “haloalkyl” refers to an alkyl, which is substituted with Cl, F, I, or Br or any combination thereof.

The term “haloalkenyl” refers to an alkenyl, which is substituted with Cl, F, I, or Br or any combination thereof.

The term “haloalkynyl” refers to an alkynyl which is substituted with Cl, F, I, or Br or any combination thereof.

The term “halogen” or “halo” refers to one or more halogen atoms, defined as F, Cl, Br, and I.

The term “hydroxycarbonyl” refers to a —C(O)—OH substituent.

The term “nitro” refers to a —NO₂ substituent.

The term “optionally substituted with” a substituent means containing 0, 1, or more of that substituent.

Unless specifically noted or clearly implied otherwise the term “about” refers to a range of values of plus or minus 10 percent, e.g. about 1 refers to the range 0.9 to 1.1.

Throughout the disclosure, reference to the compounds of Formula I is read as also including diastereomers, enantiomers, and mixtures thereof. In another embodiment, Formula (I) is read as also including salts or hydrates thereof. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, and hydroiodide.

It is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, roots, and/or seeds.

Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.

In one embodiment, a compound of Formula (I) is provided:

wherein:

X is H or C(O)R₅;

Y is H, C(O)R₅, or Q;

Q is

R₁ is H, alkyl, alkenyl, aryl, —C(O)R₄, each optionally substituted with one or more R₄;

R₂ is H, alkyl, alkenyl, aryl —C(O)R₄, each optionally substituted with one or more R₄;

R₃ is H, —C(O)R₆ or —CH₂OC(O)R₆;

R₄ is alkyl, alkenyl, halo, haloalkyl, alkoxy, or aryl;

R₅ is alkyl, alkoxy, benzyl, benzyloxy, each optionally substituted with one or more R₇, wherein each R₇ may be optionally substituted with one or more R₄;

R⁶ is alkyl or alkoxy, each optionally substituted with one or more R₄;

R⁷ is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl, carbocyclic, heterocyclic, and —Si(R₄)₃, —C(O)R₄, —S(O)_(n)R₄, each optionally substituted with one or more R⁴;

with the proviso that when R₁ and R₂ are H, X and Y are C(O)R₅ and R₅ is tert-butoxy.

In one more particular embodiment, X and Y are independently chosen from H or C(O)R₅. In an even more particular embodiment, X and Y are C(O)R₅ and R₅ is independently chosen from alkyl, alkoxy, benzyl, or benzyloxy, each optionally substituted with one or more R₇, wherein each R₇ may be optionally substituted with one or more R⁴. In a still more particular embodiment, R₁ and R₂ are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R₄, each optionally substituted with one or more R₄.

In one embodiment, R₅ is alkoxy and R₁ and R₂ are H.

In one embodiment, R₅ is tert-butoxy. In one embodiment, X and Y are hydrogen. In a more particular embodiment, R₁ and R₂ are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R₄, each optionally substituted with one or more R₄.

In one embodiment, R₁ and R₂ are independently alkyl, alkenyl, aryl, or —C(O)R₄, each optionally substituted with one or more R₄.

In one embodiment, R₁ and R₂ are independently alkyl or aryl, each optionally substituted with one or more R₄.

In one embodiment, the amine is protonated to give an ammonium salt of a mineral acid independently chosen from hydrogen chloride, hydrogen bromide, or hydrogen iodide. In a more particular embodiment, the ammonium salt is the ammonium hydrochloride.

In one embodiment, X is H and Y is Q.

In one embodiment, R₁ and R₂ are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R₄, each optionally substituted with one or more R₄.

In one embodiment, R₁ and R₂ are independently alkyl, alkenyl, aryl, or —C(O)R₄, each optionally substituted one or more R₄.

In one embodiment, R₁ and R₂ are independently alkyl or aryl, each optionally substituted with one or more R₄.

In one embodiment, R₃ is H, —C(O)R₆ or —CH₂C(O)R₆. In a more particular embodiment, R₃ is H. In another more particular embodiment, R₃ is C(O)R₆. In a further particular embodiment, R₆ is alkyl or alkoxy, each optionally substituted with one or more R₄. In another further particular embodiment, R₆ is alkyl, optionally substituted with one or more R₄. In still another further particular embodiment, R₆ is —CH₃ or —CH₂CH₂—R₄ and R₄ is OCH₃. In another more particular embodiment, R₃ is —CH₂OC(O)R₆. In a further particular embodiment, R₆ is alkyl or alkoxy, each optionally substituted with one or more R₄. In another further particular embodiment, R₆ is alkyl, each optionally substituted with one or more R₄. In still another more particular embodiment, R₆ is —CH₃ or —CH(CH₃)₂.

In one embodiment, a composition is provided for the control of a fungal or fugal like pathogen. In one embodiment, the composition includes the compound of Formula I as defined by any of the above embodiments and a phytologically acceptable carrier material. The combination of Formula I and the carrier is useful for the control of fungal and fungal like pathogens. In a more particular embodiment, the fungal or fungal like pathogen is selected from the group consisting of: Mycosphaerella graminicola(Septoria tritici), Puccinia triticina, Puccinia striiformis, Venturia inaequalis, Uncinula necator, Rhynchosporium secalis, Magnaporthe grisea, Phakopsora pachyrhizi, Leptosphaeria nodorum, Blumeria graminis f. sp. tritici, Blumeria graminis f. sp. hordei, Erysiphe cichoracearum, Glomerella lagenarium, Cercospora beticola, and Alternaria solani. In a further particular embodiment, the fungal pathogen or fungal like pathogen is selected from the group consisting of: Septoria tritici and Puccinia triticina.

In one embodiment, a method for the control and prevention of plant disease is provided. The method includes applying a fungicidally effective amount of at least one of the compounds of Formula I as defined by any of the above embodiments to at least one surface selected from the group consisting of: at least one surface of a plant, an area adjacent to a plant, soil in contact with a plant, soil adjacent to a plant, seeds, and equipment for use in agriculture. In a more particular embodiment, the fungicidally effective amount Formula I is applied to a surface in the range of about 0.01 g/m² to about 0.45 g/m² of Formula I.

DESCRIPTION

The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots, seeds or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, suspension concentrates, or emulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations may be prepared according to procedures that are conventional in the agricultural chemical art.

The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.

Wettable powders, which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soy bean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.

The compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.

Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.

The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%)+emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C₉-C₁₁ alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG (400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. patent application Ser. No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.

The formulations may optionally include combinations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:100 to 100:1.

The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenylsuccinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.

Additionally, the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluoron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluoron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.

Additionally, the compounds described herein be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, fluorochloridone, fluoroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluoron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.

Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, seed or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.

The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.

It will be understood by those in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Mycosphaerella graminicola; impect stage: Septoria tritici), brown rust (Puccinia triticina), stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), blister smut of maize (Ustilago maydis), powdery mildew of grapevine (Uncinula necator), leaf blotch of cereals (Rhynchosporium secalis), blast of rice (Magnaporthe grisea), downy mildew of cucurbits (Pseudoperonospora cubensis), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f. sp. tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Glomerella lagenarium), leaf spot of beet (Cercospora beticola), early blight of eggplant (Alternaria solani), and net blotch of barley (Pyrenophora teres). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.

The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term “disease-inhibiting and phytologically acceptable amount” refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m²). Fungicidally effective amount of the compounds include amounts sufficient to kill or control true fungi, pseudo-fungi, and related organisms including water moulds.

Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.

General Schemes

The following schemes illustrate approaches to generating picolinamide compounds of Formula (I). It may be understood by those skilled in the art that R₁ and R₂ may be differentially substituted through sequential derivatizations, such as an arylation reaction followed by an allylation reaction. The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns. The derivatizations that result in differential substitution at R₁ and R₂ are designated as “Derivatization Type”, wherein n=1 or 2. For example, “Arylation¹” indicates that the first derivatization performed is an arylation reaction and “Allylation²” denotes that the derivatization being performed second in the sequence is an allylation reaction. Additionally, this convention is applied to the structures throughout the schemes as well. For example, the structure below indicates that R₁ is an aryl substituent that was installed as the first derivatization of the diol, i.e. R₁ and R₂═H, and that R₂ is an allyl substituent that was installed as the second derivatization of a mono-substituted alcohol, i.e. R₁=aryl and R₂═H.

Compounds of Formulas 1.6, 1.7, 1.8, 1.9, 1.10, and 1.11 (shown below), wherein R₅ are previously defined within the scope of this disclosure, may be prepared as shown in Scheme 1. In step a of Scheme 1, treatment of a 3,4-dihydropyran of Formula 1.1, prepared as in Nicolaou, K. C. et al. J. Am. Chem. Soc., 2004, 126, 6234-6235, with ozone in the presence of a base, such as sodium bicarbonate (NaHCO₃), in a mixture of a halogenated solvent such as dichloromethane (CH₂Cl₂) and an alcoholic solvent such as methanol (MeOH), followed by treatment with a biphasic mixture of an aqueous solution of a base, such as LiOH, and a polar aprotic solvent such as tetrahydrofuran (THF) provides the compound of Formula 1.2. In step b of Scheme 1, the compound of Formula 1.2 may be treated with an glide, such as that which is generated from methyltriphenyl phosphonium bromide and a base such as n-butyl lithium, to produce a compound of Formula 1.3. In step c of Scheme 1, the compound of Formula 1.3 may be protected as an ester, such as an acetate, by treating with an acylating agent such as acetyl chloride or acetic anhydride in the presence of an organic base, such as triethylamine (TEA), in a halogenated solvent, such as CH₂Cl₂, to afford a compound of Formula 1.4. In step d of Scheme 1, the compound of Formula 1.4 may be treated with an alkylborane reagent, such as 9-borabicyclo[3.3.1]nonane (9-BBN), in a polar aprotic solvent such as THF, at a temperature between ambient temperature and 50° C. Treatment of the resulting mixture between ambient temperature and 55° C. with an aqueous solution of a base, such as potassium phosphate, a brominated olefin, such as the compound of Formula 1.5, wherein R5 is tert-butoxy, prepared as in Singh, Janak et al. Organic Letters, 2003, 5(17), 3155-3158, and a catalyst, such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (PdCl₂(dppf) affords the compound of Formula 1.6. In step e of Scheme 1, treatment of the compound of Formula 1.6 with hydrogen (15-200 psi) in the presence of a catalyst, such as 1,2-bis[(2S,5S)-2,5-diethyl-phospholano]benzene(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate ((S,S)-Et-DUPHOS-Rh), in an alcoholic solvent such as MeOH, afforded a compound of Formula 1.7. In step f of Scheme 1, treatment of the compound of Formula 1.7 with a base such as lithium hydroxide (LiOH) in a mixture of water and an alcoholic solvent such as MeOH produced a compound of Formula 1.8. In step g of Scheme 1, a solution of a compound of Formula 1.8 in a halogenated solvent such as CH₂Cl₂ or an aromatic solvent such as toluene may be added over a period of 4-12 hours (h) to a mixture of a base such as 4-dimethylaminopyridine (DMAP) and an anhydride such as 2-methyl-6-nitrobenzoic anhydride (MNBA) in either a halogenated solvent such as CH₂Cl₂ or an aromatic solvent such as toluene to generate a compound of Formula 1.9. In step h of Scheme 1, a compound of Formula 1.9 may be protected with a group such as a carbamate, for example a tert-butylcarbamate, by treating with an alkyl, alkylaryl, haloalkyl, or an aryl dicarbonate such as di-tert-butyl dicarbonate in the presence of a base, such as DMAP, in a polar aprotic solvent such as acetonitrile (CH₃CN), to afford a compound of Formula 1.10. In step i of Scheme 1, treatment of a solution of a compound of Formula 1.10 in a solvent such as ethyl acetate (EtOAc) with hydrogen gas (15-55 psi) in the presence of a palladium catalyst, such as 5% or 10% w/w palladium on carbon (Pd/C), affords a compound of Formula 1.11.

Arylation⁽¹⁾

Phenoxy compounds of Formulas 2.1, 2.2, and 2.3, wherein R₁, R₂, and R₅ are previously defined within the scope of this disclosure, may be prepared as shown in step a of Scheme 2. In step a, treatment of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R₁ and R₂ are hydrogen, with a triarylbismuth reagent, prepared according to the methods described by Hassan, A. et. al. Organometallics 1996, 15, 5613-5621, Moiseev, D. V. et al. J. Organomet. Chem. 2005, 690, 3652-3663, or Sinclair, P. J. et al. Bioorg. Med. Chem. Lett. 1995, 5, 1035-1038, in the presence of a copper catalyst, for example diacetoxycopper, and an aromatic solvent such as toluene at ambient or an elevated temperature, such as 40° C., affords a mixture of the arylated products of Formulas 2.1, 2.2, and 2.3.

Allylation⁽¹⁾

Alkoxy compounds of Formulas 3.4, 3.5, and 3.6, wherein R₁, R₂, and R₅ are previously defined within the scope of this disclosure, may be prepared as shown in steps a and b of Scheme 3. In step a, treatment of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R₁ and R₂ are hydrogen, with an allyl carbonate, such as a tert-butyl (allyl) carbonate or a symmetric (allyl) carbonate, such as bis(2-methallyl) carbonate, in the presence of a palladium catalyst and ligand, for example tris(dibenzylideneacetone)dipalladium(0) (Pd₂(dba)₃) and 1,1′-bis(diphenylphosphino)-ferrocene (dppf), in a polar aprotic solvent like THF at an elevated temperature, such as 60° C., affords a mixture of the allyloxy products of Formulas 3.1, 3.2, and 3.3. Subsequently, the allyloxy compounds may be reduced, as shown in step b, to the corresponding alkoxy compounds of Formulas 3.4, 3.5, and 3.6, wherein R₁, R₂, and R₅ are previously defined, under standard catalytic hydrogenation conditions. For example, stirring solutions of compounds of Formulas 3.1, 3.2, or 3.3 in a solvent like EtOAc with a palladium catalyst, such as 5% or 10% w/w Pd/C, under an atmosphere of hydrogen affords the alkoxy compounds of Formulas 3.4, 3.5, and 3.6. In step c, mono-substituted compounds of Formulas 3.3 or 3.6 may be treated with an alkylating reagent, such as trimethyloxonium tetrafluoroborate, in the presence of a base, such as Proton Sponge®, in a solvent such as CH₂Cl₂ to afford the di-substituted compounds of Formula 3.7, wherein R₁, R₂, and R₅ are as previously defined. Compounds of Formula 3.7, where R₂ is allyl, may be subsequently reduced under the conditions previously disclosed in step b to afford compounds of Formula 3.5.

Acylation⁽¹⁾

Acyloxy compounds of Formula 4.1, wherein R₁, R₂, and R₅ are previously defined herein, may be prepared as shown in step a of Scheme 4. In step a, treatment of a solution of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R₁ and R₂ are hydrogen, with a base such as 4-dimethylaminopyridine (DMAP) in a solvent such as CH₂Cl₂, followed by treatment with an acid chloride affords the acyloxy compound of Formula 4.1.

Arylation⁽²⁾

Disubstituted compounds of Formula 5.3 and 5.4, wherein R₁, R₂, and R₅ are previously defined within the scope of this disclosure, may be prepared as illustrated in step a of Scheme 5. Arylation of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 5.1 and 5.2, wherein R₂ is hydrogen and R₁ is hydrogen respectively, may be accomplished using the copper catalyzed triarylbismuth conditions previously disclosed in step a of Scheme 2.

Allylation⁽²⁾

Disubstituted compounds of Formula 6.3, 6.4, 6.5, and 6.6, wherein R₁, R₂, and R₅ are previously defined within the scope of this disclosure, may be prepared as illustrated in steps a and b of Scheme 6. Allylation of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 6.1 and 6.2, wherein R₂ is hydrogen and R₁ is hydrogen respectively, may be accomplished using the palladium catalyzed allylation conditions previously disclosed in step a of Scheme 3 to give the disubstituted compounds of Formula 6.3 and 6.4, wherein R₁, R₂, and R₅ are previously defined. Subsequent palladium catalyzed hydrogenation of compounds of Formulas 6.3 and 6.4, as previously disclosed in step b of Scheme 3, affords compounds of Formulas 6.5 and 6.6. Alternatively, disubstituted compounds of Formula 6.5 and 6.6, wherein R₁, R₂, and R₅ are previously defined, can be obtained from monosubstituted compounds of Formulas 6.1 and 6.2, wherein R₂ is hydrogen and R₁ is hydrogen respectively, via direct alkylation as disclosed in step c of Scheme 3.

Acylation⁽²⁾

Disubstituted compounds of Formulas 7.3 and 7.4, wherein R₁, R₂, and R₅ are previously defined herein, may be prepared as illustrated in step a of Scheme 7. Acylation of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 7.1 and 7.2, wherein R₂ is hydrogen and R₁ is hydrogen respectively, may be accomplished by treating solutions of the compounds in CH₂Cl₂ with an organic base, such as pyridine, followed by treatment with an acid chloride to give the disubstituted compounds of Formulas 7.3 and 7.4, wherein R₁, R₂, and R₅ are previously defined.

Conjugate Addition

Disubstituted compounds of Formulas 8.7 and 8.8, wherein R₁, R₂, and R₅ are previously defined within the scope of this disclosure, may be prepared as illustrated in steps a, b, and c of Scheme 8. Addition of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 8.1 and 8.2, wherein R₂ and R₁ are hydrogen respectively, into conjugated alkynes, such as but-3-yn-2-one, may be accomplished by treating solutions of the compounds in a solvent such as CH₂Cl₂ with a catalytic amount of 1,4-diazabicyclo[2.2.2]octane (DABCO), followed by addition of the conjugated alkyne at a reduced temperature, for example 0° C., to afford mixtures of E and Z isomers of the conjugate addition products of Formulas 8.3 and 8.4, as shown in step a. Subjecting the olefinic compounds of Formulas 8.3 and 8.4 to the catalytic hydrogenation conditions previously disclosed in step b of Schemes 3, as shown in step b, affords the alkoxy-ketones of Formulas 8.5 and 8.6, wherein R₁, R₂ and R₅ are previously defined within the scope of this application. Subsequent reduction of the ketones may be accomplished through treatment of the compounds of Formulas 8.5 or 8.6 in an alcohol, such as MeOH with a reducing agent, such as sodium borohydride (NaBH₄). Alkylation of the resulting diastereomeric mixtures of the hydroxyl intermediates may be achieved by treating the alcohols with an amine base, such as 1,8-Bis(dimethylamino)naphthalene (Proton Sponge®), in a solvent such as CH₂Cl₂, followed by an alkylating agent, for example trimethyloxonium tetrafluoroborate, to give compounds of Formulas 8.7 and 8.8, as shown in step c of Scheme 8.

Deprotection and Amide Formation

Picolinamide compounds of Formula 9.3, wherein R₁, R₂, X, and Y are previously defined herein, may be prepared as illustrated in steps a and b of Scheme 9. Amine salts of Formula 9.2, may be prepared by treating a solution of a bis-carbamate protected amine of Formula 9.1, wherein R5 is tert-butoxy and R₁ and R₂ are previously defined within the scope of this disclosure, in a halogenated solvent, such as CH₂Cl₂ or chloroform (CHCl₃), or neat, with a solution of a mineral acid, for example hydrogen chloride (HCl) in a solvent such as dioxane, to give the HCl salts of compounds of Formula 9.2, as shown in step a. In step b, solutions of compounds of Formula 9.2, wherein R₁ and R₂ are previously defined, are treated with 3-methoxy-4-hydroxypicolinic acid and an excess of an organic base, such as diisopropylethyl amine or N-methylmorpholine, followed by a peptide coupling reagent, for example benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) or (dimethylamino)-N,N-dimethyl(3H-[1,2,3]triazolo[4,5-b]pyridin-3-yloxy)methaniminium hexafluorophosphate (HATU), in a halogenated solvent such as CH₂Cl₂ to give compounds of Formula 9.3, wherein X is hydrogen, Y is Q, and R₁ and R₂ are as defined within the scope of this disclosure.

Hydroxypyridine Substitution

Picolinamide compounds of Formula 10.2, wherein R₁, R₂, and R₃ are previously defined herein, may be prepared as illustrated in methods a or b of Scheme 10. Treating picolinamide compounds of Formula 10.1, wherein R₃ is hydrogen and R₁ and R₂ are previously defined, with an organic base such as TEA and a catalyst, such as DMAP, in a halogenated solvent like CH₂Cl₂, followed by an acid chloride, for example acetyl chloride or 3-methoxypropanoyl chloride, affords compounds of Formula 10.2, as shown in method a. Alternatively, method b illustrates that treating picolinamide compounds of Formula 10.1, wherein R₃ is hydrogen and R₁ and R₂ are previously defined, with a carbonate base, such as sodium or potassium carbonate (Na₂CO₃ or K₂CO₃), with or without the addition of a catalytic amount of sodium iodide (NaI) in a solvent like acetone, followed by an alkyl halide, such as bromomethylacetate, chloromethylisobutyrate, or chloromethyl 2-ethoxyacetate (as prepared in Meyer, K. G.; Bravo-Altamirano, K.; Renga, J. M.; Herrick, J.; Nugent, B. M.; Boebel, T. A.; Li, F.; Wang, N. X.; Owen, W. J.; Graupner, P. R.; Yao, C.; Heemstra, R. J. Preparation of N-macrocyclyl picolinamides as fungicides. US 20130296375, Nov. 7, 2013) also affords picolinamide compounds of Formula 10.2, wherein R₁, R₂, and R₃ are previously defined within the scope of this disclosure.

Acetal Formation

Acetal compounds of Formula 11.0, wherein R₅ is previously defined within the scope of this disclosure and R₁ is aryl, alkyl or alkenyl, may be prepared as shown in Scheme 11. In Scheme 11, treatment of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R₁ and R₂ are hydrogen and R₅ is tert-butoxy, with an aldehyde, such as benzaldehyde, in the present of an acid catalyst, for example p-toluenesulfonic acid, and a dessicant, such as magnesium sulfate (MgSO₄), in a solvent such as CH₂Cl₂ or toluene at ambient temperature, affords the acetal product of Formula 11.0, where and R₁ and R₅ are as defined above.

Aryl Functionalization

Functionalized compounds of Formula 12.2, wherein R₁ is aryl, R₂ is alkyl, and R₅ is as previously defined within the scope of this disclosure, and compounds of Formula 12.5, wherein R₁ is alkyl, R₂ is aryl, and R₅ is as previously defined within the scope of this disclosure, may be prepared as illustrated in Scheme 12, steps a and b. In step a, treatment of the aryl ethers of Formulas 12.0 and 12.3, wherein R₁, R₂, and R₅ are as defined above, with a halogenating agent, such as N-bromosuccinimide (NBS), in an aprotic solvent such as CH₂Cl₂ at ambient temperature affords the halogenated compounds of Formulas 12.1 and 12.4, wherein R₁, R₂, and R₅ are as defined above. In step b, the halogenated aryl ethers of Formulas 12.1 and 12.4, wherein R₁, R₂, and R₅ are as defined above, may be cross-coupled with a boronic acid or boronate ester, such as phenyl boronic acid, in the presence of a base, such as Na₂CO₃ and a palladium catalyst, such as tetrakis(triphenylphosphine)palladium(0) (Pd(PPh₃)₄), in a mixed solvent system, for example dioxane/water, at an elevated temperature, such as 80° C., to give compounds of Formulas 12.2 and 12.5, wherein R₁, R₂, and R₅ are as defined above and R₄ is alkyl, aryl, or alkenyl.

The following examples are presented to illustrate the various aspects of the compounds of the present disclosure and should not be construed as limitations to the claims.

EXAMPLES Example 1 Preparation of (2S,3R,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diol (C1)

To a solution of (2S,3S,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diyl diacetate (32.10 grams (g), 150 millimole (mmol)) in MeOH (150 milliliters (mL)) was added K₂CO₃ (2.07 g, 15.0 mmol). This mixture was stirred for 16 h at 20° C. The resulting yellow solution was filtered through a plug of silica gel, 6 centimeters (cm)×2 cm, that was flushed with EtOAc (500 mL). The solvent was concentrated to provide (2S,3R,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diol (19.9 g, 102% yield with 95% purity resulting in 97% corrected yield) as a yellow solid, which was used without further purification: ¹H NMR (400 MHz, CDCl₃) δ 6.31 (dd, J=6.0, 1.6 Hz, 1H), 4.70 (dd, J=6.0, 2.1 Hz, 1H), 4.21 (dt, J=7.4, 1.9 Hz, 1H), 3.85 (dq, J=9.9, 6.3 Hz, 1H), 3.41 (dd, J=9.9, 7.4 Hz, 1H), 1.38 (d, J=6.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 144.82, 102.65, 75.64, 74.36, 70.34, 17.09; EIMS m/z 130 ([M⁺]).

Example 2 Preparation of (2S,3S,4S)-3,4-bis(benzyloxy)-2-methyl-3,4-dihydro-2H-pyran (C2)

Sodium hydride, 60% dispersion in mineral oil, (NaH; 14.68 g, 367 mmol) was added to a 1 liter (L), 3-neck round bottomed flask under nitrogen. The NaH dispersion was washed with hexanes (100 mL and 50 mL) and then suspended in anhydrous N,N-dimethylformamide (DMF; 230 mL) and cooled to 0° C. in an ice water bath. The flask was fitted with a 125 mL addition funnel that was then charged with (2S,3R,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diol (19.9 g, 153 mmol) as a solution in anhydrous DMF (70 mL). The diol solution was added to the NaH suspension dropwise with modification of the flow rate to mitigate the reaction rate and frothing. The addition took a total of 15 minutes (min). This mixture was then stirred at 0° C. for a further 30 min. The addition funnel was charged with benzyl bromide (40.0 ml, 336 mmol) that was added dropwise over 10 min. The mixture was then allowed to slowly warm to 20° C. over 16 h. The reaction was quenched by the slow and careful dropwise addition of saturated aqueous ammonium chloride (NH₄Cl) solution (20 mL), poured into methyl-t-butyl ether (MTBE; 900 mL), washed with water (600 mL) and saturated aqueous sodium chloride (NaCl, brine) solution (300 mL), dried over MgSO₄, filtered, and concentrated to provide a yellow oil (49.32 g, 99%; adjusted for 22 mol % residual DMF): IR (thin film) 3063, 3030, 2975, 2870, 1645, 1496, 1453, 1236, 1099, 1054, 733, 695 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.54-7.26 (m, 10H), 6.36 (dd, J=6.1, 1.1 Hz, 1H), 4.95-4.80 (m, 2H), 4.80-4.62 (m, 2H), 4.57 (d, J=11.7 Hz, 1H), 4.21 (dt, J=6.5, 1.9 Hz, 1H), 3.95 (dq, J=8.9, 6.4 Hz, 1H), 3.49 (dd, J=8.9, 6.5 Hz, 1H), 1.38 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 144.82, 138.44, 138.29, 128.45, 128.00, 127.79, 127.67, 100.17, 79.55, 74.11, 74.00, 70.58, 17.54.

Example 3 Preparation of (3R,4S,5S)-3,4-bis(benzyloxy)-5-methyltetrahydrofuran-2-ol (C3)

To a solution of (2S,3S,4S)-3,4-bis(benzyloxy)-2-methyl-3,4-dihydro-2H-pyran (41.8 g, 135 mmol) in CH₂Cl₂ (405 mL) and MeOH (50 mL) was added NaHCO₃ (1.13 g, 13.5 mmol). This mixture was cooled to −78° C. (dry ice/acetone bath) and a stream of ozone was passed through the reaction until the solution took on a blue color (2 h). Oxygen was passed through until the blue color disappeared (10 min) and then dimethyl sulfide (19.9 ml, 269 mmol) was added. The solution was warmed to 20° C. and stirred overnight. The reaction was filtered through a plug of Celite® and concentrated to provide an oil. This oil was dissolved in THF (300 mL), a solution of LiOH (9.68 g, 404 mmol) in water (150 mL) was added, and the mixture was stirred vigorously at 20° C. for 2.5 h. The phases were separated and the aqueous phase was extracted with EtOAc (2×100 mL). The combined organic extracts were washed with saturated aqueous NaCl solution (100 mL), dried over MgSO₄, filtered, and concentrated to provide a yellow oil. Purification by automated silica gel column chromatography (5→30% acetone/hexanes) provided (3R,4S,5S)-3,4-bis(benzyloxy)-5-methyltetrahydrofuran-2-ol (34.1 g, 80%) as a yellow oil. The product exists as an inseparable mixture of isomers: IR (neat film) 3402, 3031, 2934, 1658, 1496, 1454, 1367, 1105, 1059, 989, 736, 697 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.45-7.25 (m, 42H), 5.37 (d, J=6.7 Hz, 3H), 5.30 (dd, J=8.5, 4.3 Hz, 1H), 4.66 (dd, J=5.3, 2.4 Hz, 1H), 4.64-4.47 (m, 16H), 4.35 (qd, J=6.4, 4.9 Hz, 3H), 3.98 (dd, J=2.5, 0.9 Hz, 3H), 3.97-3.89 (m, 2H), 3.80 (d, J=8.5 Hz, 1H), 3.77-3.72 (m, 1H), 3.66 (ddd, J=4.8, 2.5, 0.7 Hz, 3H), 3.40 (d, J=6.7 Hz, 3H), 1.34 (d, J=6.4 Hz, 3H), 1.31 (d, J=6.4 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃) δ 137.73, 137.48, 137.42, 137.05, 128.63, 128.57, 128.52, 128.50, 128.24, 128.08, 127.98, 127.94, 127.91, 127.82, 127.81, 127.69, 127.00, 100.88, 95.90, 87.42, 87.31, 86.68, 83.14, 78.65, 76.43, 72.67, 72.19, 71.97, 65.37, 20.84, 19.38.

Example 4 Preparation of (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-ol (C4)

To a suspension of methyltriphenylphosphonium bromide (75.0 g, 211 mmol) in anhydrous THF (400 ml) under nitrogen at 0° C. (ice water bath) in a 1000 mL, 3-neck round bottom flask was added a 2.5 molar (M) solution of n-butyllithium in hexane (n-BuLi; 81.0 ml, 202 mmol) dropwise via syringe, keeping the internal temperature below 15° C. The resulting red solution was stirred at 0° C. for 45 min and then cooled to −78° C. (dry ice/acetone bath). A solution of (3R,4S,5S)-3,4-bis(benzyloxy)-5-methyltetrahydrofuran-2-ol (26.5 g, 84 mmol) in anhydrous THF (20 mL) was added via syringe and the solution was stirred for 30 min at −78° C., and then removed from the cold bath and stirred at 20° C. for 16 h. The reaction was quenched with saturated aqueous NH₄Cl solution (200 mL), diluted with water (200 mL) and diethyl ether (Et₂O; 400 mL). The phases were separated and the aqueous phase was extracted with Et₂O (2×200 mL). The combined organic phases were dried over MgSO₄, filtered, and concentrated to provide an orange oil. Purification by automated silica gel column chromatography (220% acetone/hexanes) provided (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-ol (20.23 g, 77%) as a yellow oil: ¹H NMR (400 MHz, CDCl₃) δ 7.45-7.25 (m, 10H), 5.92 (ddd, J=17.2, 10.6, 7.6 Hz, 1H), 5.44-5.25 (m, 2H), 4.75 (d, J=11.6 Hz, 1H), 4.70-4.54 (m, 2H), 4.38 (d, J=11.8 Hz, 1H), 4.12-3.99 (m, 1H), 3.91 (h, J=6.3 Hz, 1H), 3.50-3.35 (m, 1H), 2.73 (d, J=5.9 Hz, 1H), 1.17 (d, J=6.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 138.31, 137.79, 134.47, 128.46, 128.37, 127.95, 127.94, 127.79, 127.72, 119.27, 83.70, 81.18, 74.07, 70.61, 67.37, 18.90; ESIMS m/z 313.5 ([M+Na]⁺).

Example 5 Preparation of (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-yl acetate (C5)

To a solution of (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-ol (800 milligrams (mg), 2.56 mmol) in CH₂Cl₂ (10 mL) at room temperature was added TEA (1.07 ml, 7.68 mmol), acetic anhydride (0.48 ml, 5.12 mmol) and DMAP (62.6 mg, 0.512 mmol). The reaction mixture was stirred at room temperature for 2 h, concentrated and purified by column chromatography on SiO₂ (0→20% EtOAc/hexanes) to yield the title compound as a colorless oil (891 mg, 98%): ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.23 (m, 10H), 5.84 (ddd, J=17.2, 10.4, 8.2 Hz, 1H), 5.38-5.26 (m, 2H), 5.02 (qd, J=6.5, 3.7 Hz, 1H), 4.83-4.67 (m, 2H), 4.61 (d, J=11.8 Hz, 1H), 4.37 (d, J=11.8 Hz, 1H), 3.84 (ddt, J=8.0, 6.3, 0.8 Hz, 1H), 3.63 (dd, J=6.3, 3.7 Hz, 1H), 1.91 (s, 3H), 1.26 (d, J=6.5 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.19, 138.64, 138.30, 135.07, 128.33, 128.25, 128.08, 127.94, 127.58, 127.52, 119.42, 82.90, 81.86, 74.98, 71.03, 70.48, 21.32, 14.75; ESIMS m/z 377.3 ([M+Na]⁺).

Example 6 Preparation of (6S,7S,8S,Z)-methyl 8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)non-2-enoate (C6)

To a solution of (2S,3S,4S)-3,4-bis(benzyloxy)oct-7-en-2-yl acetate (931 mg, 2.63 mmol) in THF (2 mL) was added 9-BBN (0.5 M solution in THF, 6.82 mL, 3.41 mmol). The reaction mixture was stirred at room temperature for 30 min, then warmed to 50° C. and stirred for 2 h. After the reaction mixture was cooled to room temperature, an aqueous solution of potassium phosphate (K₃PO₄; 3 M, 1.75 mL, 5.25 mmol), a solution of (Z)-methyl 3-bromo-2-((tert-butoxycarbonyl)amino)acrylate (736 mg, 2.63 mmol) in DMF (9 mL, degassed), and PdCl₂(dppf) (96 mg, 0.13 mmol) was added. The reaction mixture was heated to 55° C. and stirred overnight, and then quenched with saturated aqueous NaHCO₃ and extracted with Et₂O. The combined organic phase was dried over sodium sulfate (Na₂SO₄), filtered, concentrated, and purified by column chromatography on SiO₂ (0→30% EtOAc/hexanes) to yield the title compound as a light yellow oil (1.26 g, 86%): IR (thin film) 3341, 2930, 1717, 1367, 1241 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.43-7.26 (m, 10H), 6.48 (t, J=7.3 Hz, 1H), 6.03 (s, 1H), 5.08 (qd, J=6.5, 3.1 Hz, 1H), 4.77-4.58 (m, 3H), 4.49 (d, J=11.2 Hz, 1H), 3.76 (s, 3H), 3.64 (dd, J=6.1, 3.1 Hz, 1H), 3.44 (ddd, J=7.9, 6.0, 4.2 Hz, 1H), 2.43-2.29 (m, 1H), 2.29-2.16 (m, 1H), 1.98 (s, 3H), 1.85-1.61 (m, 2H), 1.44 (s, 9H), 1.31 (d, J=6.5 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.32, 165.29, 153.24, 138.41, 138.31, 135.67, 128.33, 128.04, 127.98, 127.68, 127.62, 81.82, 80.45, 79.30, 74.33, 73.15, 71.22, 70.56, 52.29, 29.54, 28.18, 24.66, 21.32, 15.09; HRMS-ESI (m/z) [M+H]⁺ calcd for C₃₁H₄₂NO₈, 556.2905; found, 556.2903.

Example 7 Preparation of (2S,6S,7S,8S)-methyl-8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)nonanoate (C7)

A solution of (6S,7S,8S,Z)-methyl 8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)non-2-enoate (120 mg, 0.216 mmol) in anhydrous MeOH (4.3 mL) was purged with N₂ for 15 min in a 250 mL stainless steel bomb. To the solution was added 1,2-bis[(2S,5S)-2,5-diethyl-phospholano]benzene(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate ((S,S)-Et-DUPHOS-Rh; 1.56 mg, 2.16 micromole (μmol)), and the vessel was sealed, purged twice with hydrogen (H₂; 200 psi), and then pressurized to 200 psi with H₂ and stirred at room temperature overnight. The reaction was concentrated and purified by column chromatography on SiO₂ (0→30% EtOAc/hexanes) to yield the title compound as a colorless oil (110 mg, 91%): ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.23 (m, 10H), 5.10-5.04 (m, 1H), 4.97 (d, J=8.4 Hz, 1H), 4.73 (d, J=11.6 Hz, 1H), 4.65 (d, J=7.7 Hz, 1H), 4.62 (d, J=7.4 Hz, 1H), 4.50 (d, J=11.4 Hz, 1H), 4.32-4.20 (m, 1H), 3.70 (s, 3H), 3.61 (dd, J=6.0, 3.1 Hz, 1H), 3.43-3.39 (m, 1H), 1.98 (s, 3H), 1.79-1.66 (m, 1H), 1.64-1.47 (m, 4H), 1.45 (s, 9H), 1.31 (d, J=6.5 Hz, 3H), 1.29-1.20 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.27, 170.24, 155.35, 138.51, 138.45, 128.33, 128.05, 128.01, 127.67, 127.63, 81.89, 79.82, 79.39, 74.30, 73.07, 71.28, 53.33, 52.21, 32.68, 30.52, 28.34, 21.34, 15.13; ESIMS m/z 580.4 ([M+Na]⁺).

Example 8 Preparation of (2S,6S,7S,8S)-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)-8-hydroxynonanoic acid (C8)

To a solution of (2S,6S,7S,8S)-methyl 8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)nonanoate (110 mg, 0.20 mmol) in MeOH (2 mL) and water (2 mL) at room temperature was added LiOH.H₂O (33.1 mg, 0.789 mmol). The reaction mixture was stirred at room temperature for 3 h, quenched with 1 Normal (N) hydrochloric acid, and extracted with EtOAc. The combined organic phases were washed with saturated aqueous NaHCO₃, dried over Na₂SO₄, filtered, and concentrated to yield the title compound as a colorless oil (96 mg, 97%): IR (thin film) 3409, 2929, 1686, 1588; ¹H NMR (400 MHz, CDCl₃) δ 7.33-7.21 (m, 10H), 5.40 (s, 1H), 4.56-4.48 (m, 4H), 3.96-3.81 (m, 2H), 3.57-3.51 (m, 1H), 3.31-3.23 (m, 1H), 1.81-1.41 (m, 6H), 1.37 (s, 9H), 1.19 (d, J=6.2 Hz, 3H); ESIMS m/z 524.4 ([M+Na]⁺).

Example 9 Preparation of tert-butyl ((3S,7S,8S,9S)-7,8-bis(benzyloxy)-9-methyl-2-oxooxonan-3-yl)carbamate (C9)

To a solution of DMAP (137 mg, 1.12 mmol) and MNBA (129 mg, 0.375 mmol) in CH₂Cl₂ (30 mL) at room temperature was added a solution of (2S,6S,7S,8S)-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)-8-hydroxynonanoic acid (94 mg, 0.19 mmol) in CH₂Cl₂ (8 mL) over 4 h via syringe pump. The reaction mixture was stirred overnight, concentrated and purified by column chromatography on SiO₂ (0→20%, EtOAc/hexanes) to yield the title compound as a colorless oil (71 mg, 78%): ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.26 (m, 10H), 5.03 (d, J=8.3 Hz, 1H), 4.88 (d, J=10.8 Hz, 1H), 4.85-4.77 (m, 1H), 4.68 (d, J=10.8 Hz, 1H), 4.61 (d, J=11.4 Hz, 1H), 4.48 (d, J=11.4 Hz, 1H), 4.20 (dt, J=10.9, 7.7 Hz, 1H), 3.67-3.57 (m, 2H), 2.26 (dt, J=13.6, 6.7 Hz, 1H), 2.21-2.09 (m, 1H), 1.77-1.60 (m, 2H), 1.44 (s, 9H), 1.41 (d, J=6.4 Hz, 3H), 1.23-1.11 (m, 1H), 0.99-0.87 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.15, 154.91, 138.40, 138.31, 128.39, 128.37, 127.94, 127.80, 127.71, 127.64, 83.90, 83.70, 79.91, 75.77, 72.76, 71.20, 52.76, 33.88, 28.32, 28.00, 18.28, 18.10; ESIMS m/z 506.3 ([M+Na]⁺).

Example 10 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C10)

A solution of tert-butyl ((3S,7S,8S,9S)-7,8-bis(benzyloxy)-9-methyl-2-oxooxonan-3-yl)carbamate (150 mg, 0.31 mmol), DMAP (19.0 mg, 0.155 mmol) and di-tert-butyl dicarbonate (271 mg, 1.24 mmol) in CH₃CN (2.1 mL) was stirred at room temperature for 18 h, concentrated, and purified by column chromatography on SiO₂ (0→15% EtOAc/hexanes) to yield the title compound (76 mg, 42%) as a colorless oil along with recovered starting material (72 mg, 48%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.27 (m, 10H), 4.88 (d, J=10.9 Hz, 1H), 4.83 (dd, J=10.4, 8.0 Hz, 1H), 4.75-4.59 (m, 3H), 4.49 (d, J=11.4 Hz, 1H), 3.69-3.57 (m, 2H), 2.42-2.33 (m, 1H), 2.24-2.14 (m, 1H), 2.08-2.00 (m, 1H), 1.79-1.65 (m, 2H), 1.51 (s, 18H), 1.41 (d, J=6.3 Hz, 3H), 1.01 (ddt, J=16.0, 7.7, 1.8 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.86, 152.91, 138.52, 138.41, 128.39, 128.36, 127.95, 127.83, 127.68, 127.60, 84.08, 83.59, 82.71, 75.65, 72.95, 71.21, 57.43, 30.55, 28.50, 27.99, 19.28, 18.23; ESIMS m/z 606.4 ([M+Na]⁺).

Example 11 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (F1)

A mixture of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (66.0 mg, 0.113 mmol) and Pd/C (5% w/w Pd, 24.1 mg, 0.011 mmol) in EtOAc (2.3 mL) was stirred under an H₂ balloon at room temperature for 7 h. The reaction mixture was filtered through Celite®, and concentrated to yield the title compound (44.0 mg, 96%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 4.83 (dd, J=10.1, 7.3 Hz, 1H), 4.72 (dq, J=9.1, 6.3 Hz, 1H), 3.58-3.42 (m, 2H), 2.84 (s, 1H), 2.45 (s, 1H), 2.35 (dtd, J=13.8, 9.8, 2.2 Hz, 1H), 2.14-2.02 (m, 1H), 1.96-1.67 (m, 3H), 1.51 (s, 18H), 1.42 (d, J=6.3 Hz, 3H), 1.31-1.21 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.77, 152.91, 82.81, 76.85, 73.86, 73.18, 57.69, 35.34, 30.93, 27.98, 20.03, 18.06; ESIMS m/z 426.3 ([M+Na]⁺).

Example 12 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (C11)

A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (1.845 g, 4.57 mmol), triphenylbismuth diacetate (3.06 g, 5.49 mmol) and diacetoxycopper (0.166 g, 0.915 mmol) in toluene (18.3 ml) was stirred at 40° C. for 1 h. The reaction mixture was filtered thru Celite®, the pad washed with toluene (2×40 mL), and the filtrate concentrated to yield 2.3 g light blue foam. Purification by column chromatography (SiO₂, 0→20% EtOAc/hexanes) yielded the title compound as a white foam (1.15 g, 52%), along with the 7-substituted and 7,8-disubstituted products: ¹H NMR (400 MHz, CDCl₃) δ 7.33-7.24 (m, 2H), 7.03 (d, J=7.9 Hz, 2H), 6.98 (t, J=7.3 Hz, 1H), 4.96-4.80 (m, 2H), 4.29 (dd, J=9.4, 7.9 Hz, 1H), 3.86 (t, J=6.7 Hz, 1H), 2.47-2.27 (m, 2H), 2.15-1.95 (m, 2H), 1.91-1.71 (m, 2H), 1.59-1.40 (m, 19H), 1.31 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.73, 159.42, 152.85, 129.69, 121.92, 116.27, 83.73, 82.78, 73.98, 72.46, 57.56, 33.41, 30.90, 27.98, 19.79, 18.31; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₅H₃₇NNaO₈, 502.2411; found, 502.2344.

The following compounds were prepared and isolated using the appropriately substituted triphenylbismuth diacetate reagents and the methodology described in Example 12:

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (C12)

Isolated as a white foam (520 mg, 24%): ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.27 (m, 2H), 7.03-6.95 (m, 1H), 6.92 (dd, J=8.7, 1.0 Hz, 2H), 4.95 (t, J=8.5 Hz, 1H), 4.84 (dq, J=9.6, 6.3 Hz, 1H), 4.24-4.12 (m, 1H), 3.86 (ddd, J=9.9, 7.8, 2.4 Hz, 1H), 2.63 (d, J=2.5 Hz, 1H), 2.38-2.20 (m, 1H), 2.13-1.98 (m, 2H), 1.89 (tt, J=11.1, 5.6 Hz, 1H), 1.65-1.54 (m, 2H), 1.51 (s, 18H), 1.47 (d, J=6.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.56, 157.12, 152.90, 129.63, 121.65, 116.60, 82.78, 82.32, 75.72, 72.93, 57.26, 31.06, 30.37, 27.98, 20.17, 18.19; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₅H₃₇NNaO₈, 502.2411; found, 502.2399.

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-7,8-diphenoxy-oxonan-3-yl]carbamate (C13)

Isolated as a white solid (172 mg, 7%): ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.14 (m, 4H), 7.04 (dd, J=8.8, 1.0 Hz, 2H), 6.97-6.86 (m, 2H), 6.86-6.77 (m, 2H), 4.98 (dd, J=9.5, 6.4 Hz, 1H), 4.91 (dd, J=10.0, 8.3 Hz, 1H), 4.62 (dd, J=9.5, 7.4 Hz, 1H), 4.52 (ddd, J=7.1, 5.2, 1.6 Hz, 1H), 2.46-2.18 (m, 2H), 2.08 (dd, J=13.5, 6.8 Hz, 1H), 1.91 (dt, J=13.0, 7.3 Hz, 1H), 1.72 (m, H), 1.52 (s, 18H), 1.41 (d, J=6.4 Hz, 3H), 1.20 (dt, J=7.7, 1.8 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.71, 159.55, 157.64, 152.85, 129.39, 129.37, 121.54, 121.35, 116.72, 116.57, 82.81, 82.37, 82.21, 72.57, 57.25, 30.54, 28.98, 27.99, 19.32, 18.32; ESIMS m/z 578.8 ([M+Na]⁺).

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-(4-fluorophenoxy)-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C14)

Isolated as a colorless oil (150 mg, 0.30 mmol, 61%): ¹H NMR (400 MHz, CDCl₃) δ 7.04-6.90 (m, 4H), 4.93-4.82 (m, 2H), 4.17 (dd, J=9.4, 7.9 Hz, 1H), 3.86 (ddd, J=8.1, 6.1, 2.4 Hz, 1H), 2.40 (dtd, J=13.7, 9.9, 3.5 Hz, 2H), 2.16-1.94 (m, 2H), 1.82 (dd, J=6.1, 3.1 Hz, 2H), 1.52 (s, 18H), 1.49-1.41 (m, 1H), 1.31 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.69, 157.76 (d, J=240.0 Hz), 155.62 (d, J=2.3 Hz), 152.85, 117.54 (d, J=8.0 Hz), 116.04 (d, J=23.2 Hz), 84.90, 82.82, 73.96, 72.30, 57.53, 33.52, 30.86, 27.97, 19.78, 18.35; ESIMS m/z 498.3 [(M+H)⁺].

Example 12A Preparation of [(3S,7S,8S,9S)-9-methyl-2-oxo-7,8-diphenoxy-oxonan-3-yl]ammonium chloride (F2)

A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-7,8-diphenoxy-oxonan-3-yl]carbamate (650 mg, 1.17 mmol) and HCl (4M in dioxane; 5.85 mL, 23.4 mmol) in CHCl₃ (6 mL) was stirred at 23° C. for 1.5 h. The solution was concentrated to yield the title compound as a white foam (458 mg, 100%), which was used without further purification.

Example 12B, Step 1 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (C15)

A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (1.075 g, 2.24 mmol), tert-butyl (2-methylallyl) carbonate (1.158 g, 6.70 mmol), dppf (0.025 g, 0.045 mmol) and Pd₂(dba)₃ (0.021 g, 0.022 mmol) in degassed THF (11.2 ml) was heated to 60° C. for 1.5 h. The solution was cooled to room temperature and purified by column chromatography (SiO₂; 0→5% EtOAc/Hex) to yield the title compound (1.0 g, 84%) as a white solid: ¹H NMR (400 MHz, CDCl₃) δ 7.34-7.17 (m, 2H), 7.09-7.02 (m, 2H), 6.98-6.90 (m, 1H), 4.94-4.72 (m, 4H), 4.43 (dd, J=9.6, 7.4 Hz, 1H), 3.91 (d, 1H), 3.79 (d, 1H), 3.62 (ddd, J=7.0, 5.1, 1.7 Hz, 1H), 2.47-2.34 (m, 1H), 2.25-2.13 (m, 1H), 2.11-2.01 (m, 1H), 1.88-1.63 (m, 2H), 1.56 (s, 3H), 1.52 (s, 18H), 1.33 (d, J=6.4 Hz, 3H), 1.07 (dd, J=16.0, 7.7 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.80, 159.58, 152.86, 142.36, 129.36, 121.24, 116.29, 112.34, 82.72, 82.53, 82.06, 73.50, 72.76, 57.39, 30.56, 28.61, 27.98, 19.40, 19.29, 18.19; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₉H₄₃NNaO₈, 556.2881; found, 556.2873.

The following compounds were prepared and isolated using the methodology described in Example 12B, Step 1:

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-8-(2-methylallyloxy)-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (C16)

Isolated as a white solid (448 mg; 85%): ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.23 (m, 2H), 6.99-6.88 (m, 3H), 4.94-4.72 (m, 4H), 4.46-4.35 (m, 1H), 4.22-4.16 (m, 1H), 4.03 (d, J=11.6 Hz, 1H), 3.67 (dd, J=9.7, 7.1 Hz, 1H), 2.38-2.25 (m, 1H), 2.25-2.10 (m, 1H), 2.04-1.95 (m, 1H), 1.83 (m 1H), 1.65 (s, 3H), 1.63-1.57 (m, 1H), 1.49 (s, 18H), 1.46 (d, J=6.3 Hz, 3H), 1.08 (dd, J=16.0, 7.8 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.75, 157.45, 152.86, 142.27, 129.49, 121.17, 116.55, 112.39, 83.08, 83.01, 82.73, 77.41, 72.73, 57.27, 30.44, 28.80, 27.98, 19.74, 19.18, 18.23; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₉H₄₃NNaO₈, 556.2881; found, 556.2875.

Example 12B, Step 2 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (C17)

A suspension of Pd/C (5% w/w Pd; 199 mg) and tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (1.00 g, 1.87 mmol) in EtOAc (9.4 mL) was stirred rapidly at room temperature under one atmosphere (atm) of H₂ overnight. The suspension was filtered through Celite®, washed with EtOAc (3×30 mL), and the combined extracts were concentrated to yield the title compound as a clear oil (980 mg, 98%): ¹H NMR (400 MHz, CDCl₃) δ 7.27-7.16 (m, 2H), 7.12-7.01 (m, 2H), 6.99-6.86 (m, 1H), 4.94-4.73 (m, 2H), 4.38 (dd, J=9.6, 7.3 Hz, 1H), 3.53 (ddd, J=7.1, 5.2, 1.7 Hz, 1H), 3.24 (dd, J=8.8, 6.6 Hz, 1H), 3.05 (dd, J=8.8, 6.3 Hz, 1H), 2.53-2.29 (m, 1H), 2.29-2.11 (m, 1H), 2.04 (s, 1H), 1.88-1.60 (m, 3H), 1.60-1.40 (m, 18H), 1.33 (d, J=6.4 Hz, 3H), 1.05 (dd, J=16.0, 7.8 Hz, 1H), 0.78 (d, J=6.7 Hz, 3H), 0.73 (d, J=6.7 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.84, 159.72, 152.86, 129.27, 121.17, 116.42, 83.13, 82.72, 82.70, 76.40, 72.72, 57.41, 30.58, 28.70, 28.49, 27.98, 19.36, 19.24, 19.21, 18.20; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₉H₄₅NNaO₈, 558.3037; found, 558.3030.

The following compounds were prepared and isolated using the methodology described in Example 12B, Step 2:

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (C18)

Isolated as a white solid (430 mg; 100%): ¹H NMR (400 MHz, CDCl₃) δ 7.32-7.22 (m, 2H), 6.99-6.86 (m, 3H), 4.86 (dd, J=10.2, 8.2 Hz, 1H), 4.75 (dq, J=9.7, 6.3 Hz, 1H), 4.43-4.26 (m, 1H), 3.66-3.50 (m, 2H), 3.36 (dd, J=8.7, 6.7 Hz, 1H), 2.44-2.24 (m, 1H), 2.24-2.08 (m, 1H), 2.04-1.91 (m, 1H), 1.89-1.56 (m, 3H), 1.53-1.46 (m, 18H), 1.44 (d, J=6.3 Hz, 3H), 1.06 (dd, J=16.0, 7.9 Hz, 1H), 0.82 (d, J=6.7 Hz, 3H), 0.78 (d, J=6.7 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.78, 157.65, 152.86, 129.44, 121.06, 116.54, 83.33, 83.06, 82.71, 80.56, 72.93, 57.27, 30.46, 28.97, 28.85, 27.97, 19.39, 19.28, 19.17, 18.15; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₉H₄₅NNaO₈, 558.3037; found, 558.2994.

Example 12B, Step 3 Preparation of [(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]ammonium chloride (F3)

Prepared according to the methods described in Example 12A.

The following compounds were prepared and isolated using the methodology described in Example 12B, Step 3:

[(3S,7S,8S,9S)-8-Isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]ammonium chloride (F4)

Example 12C, Step 1 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-(4-fluorophenoxy)-7-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]carbamate (C19)

To a stirred solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-(4-fluorophenoxy)-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (150 mg, 0.30 mmol) in toluene (1.51 mL) under N₂ was added tri(p-methoxyphenyl)bismuth diacetate (391 mg, 0.603 mmol) followed by diacetoxycopper (10.9 mg, 0.060 mmol) and N-cyclohexyl-N-methylcyclohexanamine (129 microliters (μL), 0.603 mmol). The reaction mixture was heated for 18 h at 43° C. The reaction was concentrated and purified by column chromatography (0→100% EtOAc/hex) to yield the title compound (75 mg, 41%) as a yellow oil: ¹H NMR (400 MHz, CDCl₃) δ 7.07-6.97 (m, 2H), 6.96-6.85 (m, 2H), 6.81-6.69 (m, 4H), 4.99-4.85 (m, 2H), 4.47 (dd, J=9.6, 7.4 Hz, 1H), 4.34 (dt, J=5.5, 3.5 Hz, 1H), 3.73 (s, 3H), 2.37 (q, J=10.7 Hz, 1H), 2.22 (ddt, J=15.4, 9.6, 5.2 Hz, 1H), 2.12-1.98 (m, 1H), 1.95-1.80 (m, 1H), 1.73 (dd, J=14.5, 7.2 Hz, 1H), 1.51 (s, 18H), 1.40 (d, J=6.4 Hz, 3H), 1.15 (dd, J=16.0, 7.7 Hz, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ −122.84; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₃₂H₄₂FNNaO₉, 626.2736; found, 626.2739.

Example 12C, Step 2 Preparation of [(3S,7S,8S,9S)-8-(4-fluorophenoxy)-7-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F5)

Prepared according to the methods described in Example 12A.

Example 13 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-8-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (C20)

A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (100 mg, 0.25 mmol), bis(2-methylallyl) carbonate (51 mg, 0.30 mmol), dppf (14 mg, 0.025 mmol) and Pd₂(dba)₃ (11.4 mg, 0.012 mmol) in degassed THF (1.24 mL) was heated to 60° C. for 1.5 h. The solution was cooled to room temperature and purified by column chromatography (SiO₂; 0→5% EtOAc/hexanes) to yield the title compound (61 mg, 54%) as a white solid: ¹H NMR (400 MHz, CDCl₃) δ 5.03-4.97 (m, 1H), 4.90 (s, 1H), 4.82 (dd, J=10.4, 7.1 Hz, 1H), 4.74 (dq, J=9.5, 6.3 Hz, 1H), 4.09 (s, 2H), 3.64-3.56 (m, 1H), 3.23 (dd, J=9.4, 7.7 Hz, 1H), 2.53 (d, J=1.5 Hz, 1H), 2.43-2.30 (m, 1H), 2.12-2.00 (m, 1H), 1.92-1.80 (m, 1H), 1.77 (m, 5H), 1.61-1.45 (m, 19H), 1.42 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.73, 152.84, 141.85, 112.38, 85.49, 82.70, 77.62, 73.37, 72.70, 57.77, 34.76, 30.87, 27.96, 19.99, 19.67, 18.23; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₃H₃₉NNaO₈, 480.2568; found, 480.2572.

The following compounds were prepared and isolated using the appropriately substituted allyl carbonate and the methodology described in Example 13:

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (C21)

Isolated as a white solid (25 mg; 22%): ¹H NMR (400 MHz, CDCl₃) δ 5.01-4.95 (m, 1H), 4.91 (s, 1H), 4.85 (dd, J=9.5, 7.6 Hz, 1H), 4.80-4.67 (m, 1H), 4.01 (d, J=12.2 Hz, 1H), 3.83 (d, J=12.2 Hz, 1H), 3.56 (ddd, J=9.5, 7.7, 2.0 Hz, 1H), 3.21 (td, J=7.6, 2.1 Hz, 1H), 2.85 (d, J=2.0 Hz, 1H), 2.40-2.23 (m, 1H), 2.13-2.00 (m, 1H), 1.93 (dt, J=14.0, 6.9 Hz, 1H), 1.84-1.73 (m, 4H), 1.70-1.56 (m, 1H), 1.51 (s, 18H), 1.46-1.38 (m, 4H); ¹³C NMR (101 MHz, CDCl₃) δ 170.74, 152.92, 141.77, 112.89, 82.69, 81.96, 75.76, 73.49, 73.25, 57.61, 31.12, 31.04, 27.98, 20.37, 19.67, 18.16; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₃H₃₉NNaO₈, 480.2568; found, 480.2576.

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (C22)

Isolated as a white solid (200 mg; 5%): ¹H NMR (400 MHz, CDCl₃) δ 5.03-4.91 (m, 2H), 4.90-4.75 (m, 3H), 4.67 (dq, J=9.0, 6.3 Hz, 1H), 4.25 (d, J=11.7 Hz, 1H), 3.99 (dd, J=21.0, 11.9 Hz, 2H), 3.90-3.79 (m, 1H), 3.56-3.35 (m, 2H), 2.44-2.27 (m, 1H), 2.12 (ddd, J=23.7, 9.0, 5.0 Hz, 1H), 2.02 (dt, J=13.3, 6.5 Hz, 1H), 1.74 (s, 3H), 1.75 (s, 3H), 1.72-1.54 (m, 3H), 1.51 (s, 18H), 1.40 (d, J=6.3 Hz, 3H), 1.03-0.91 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.86, 152.90, 142.54, 142.48, 112.09, 111.94, 83.62, 82.67, 73.10, 72.99, 57.43, 30.55, 28.52, 27.98, 19.80, 19.70, 19.24, 18.12; EIMS m/z 534.8 ([M+Na]⁺)

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-cyclopent-2-en-1-yloxy-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C23)

Isolated as a yellow foam (344 mg, 41%): IR (neat) 3520, 2978, 2928, 1744, 1704, 1358 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 6.09-6.04 (m, 1H), 5.96 (dq, J=5.9, 2.1 Hz, 0.5H), 5.86 (dq, J=5.8, 2.2 Hz, 0.5H), 4.88-4.63 (m, 3H), 3.55-3.39 (m, 1H), 3.34-3.28 (m, 1H), 2.61-1.99 (m, 7H), 1.92-1.69 (m, 4H), 1.51 (s, 18H), 1.44 (d, J=6.4 Hz, 1.5H), 1.42 (d, J=6.4 Hz, 1.5H); ESIMS m/z 492.3 ([M+Na]⁺).

Example 13A, Step 1 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7,8-diisobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C24)

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (333 mg, 0.651 mmol) in EtOAc (6.51 mL) was added Pd/C (10% w/w Pd, 34.6 mg, 0.033 mmol). The atmosphere was replaced with 1 atm hydrogen (balloon) and the reaction was stirred overnight at room temperature. The reaction mixture was filtered through Celite® and the pad was flushed with EtOAc. The filtrate was concentrated to provide the title compound (313 mg, 93%) as a white, crystalline solid: IR (thin film) 2957, 1742, 1724, 1470, 1366, 1347, 1245, 1104 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 4.80 (dd, J=10.5, 8.0 Hz, 1H), 4.69-4.54 (m, 1H), 3.60 (dd, J=8.6, 6.2 Hz, 1H), 3.40-3.21 (m, 4H), 3.11 (dd, J=8.7, 6.3 Hz, 1H), 2.42-2.25 (m, 1H), 2.20-2.05 (m, 1H), 2.01 (m, 1H), 1.81 (tt, J=12.7, 6.3 Hz, 2H), 1.73-1.55 (m, 3H), 1.51 (s, 18H), 1.42-1.32 (m, 3H), 1.01-0.80 (m, 12H); ¹³C NMR (101 MHz, CDCl₃) δ 170.91, 152.89, 84.27, 83.65, 82.64, 80.41, 75.84, 73.15, 57.46, 30.53, 29.07, 28.89, 28.20, 27.98, 19.58, 19.54, 19.39, 19.18, 18.12.

Example 13A, Step 2 Preparation of [(3S,7S,8S,9S)-7,8-diisobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F6)

Prepared according to the methods described in Example 12A.

Example 13B, Step 1 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C25)

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (1.00 g, 2.19 mmol) in EtOAc (4 mL) in a vial was added Pd/C (5% w/w Pd, 0.233 g). The vial was evacuated and backfilled with hydrogen (1 atm), then stirred vigorously at room temperature. After stirring overnight, the reaction mixture was filtered through a pad of Celite® and concentrated to yield a white solid (1.06 g, 95%): IR (thin film) 3448, 3224, 2960, 2934, 2877, 1752, 1742, 1723, 1139, 1119 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 4.85 (dd, J=9.4, 7.4 Hz, 1H), 4.73 (dq, J=9.5, 6.3 Hz, 1H), 3.51 (ddd, J=9.5, 7.6, 1.8 Hz, 1H), 3.35 (dd, J=8.9, 6.7 Hz, 1H), 3.11 (dd, J=8.8, 6.3 Hz, 2H), 2.93 (d, J=1.8 Hz, 1H), 2.30 (dtd, J=14.0, 9.8, 1.9 Hz, 1H), 2.13-2.00 (m, 1H), 1.95-1.74 (m, 3H), 1.68-1.61 (m, 1H), 1.61-1.58 (m, 1H), 1.51 (s, 18H), 1.42 (d, J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 1.2 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 170.77, 152.92, 82.71, 82.40, 76.26, 75.85, 73.63, 57.69, 31.43, 31.22, 28.69, 27.99, 20.52, 19.41, 19.36, 18.19; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₃H₄₁NNaO₈, 482.2724; found, 482.2718.

The following compounds were prepared and isolated using the methodology described in Example 13B, Step 1:

tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-8-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C26)

Isolated as a colorless oil (600 mg, 100%): ¹H NMR (400 MHz, CDCl₃) δ 4.81 (dd, J=10.5, 6.9 Hz, 1H), 4.77-4.66 (m, 1H), 3.60-3.50 (m, 1H), 3.47 (dd, J=8.6, 6.3 Hz, 1H), 3.40 (dd, J=8.6, 6.7 Hz, 1H), 3.12 (dd, J=9.5, 7.7 Hz, 1H), 2.63-2.56 (m, 1H), 2.36 (ddt, J=13.7, 11.1, 4.9 Hz, 1H), 2.12-1.98 (m, 1H), 1.95-1.75 (m, 4H), 1.53-1.50 (m, 1H), 1.51 (s, 18H), 1.41 (d, J=6.3 Hz, 3H), 0.93 (dd, J=6.7, 3.3 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 170.72, 152.82, 85.27, 82.67, 80.81, 72.95, 72.82, 57.87, 35.34, 30.89, 29.03, 27.95, 20.13, 19.33, 19.23, 18.26.

Example 13B, Step 2 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-8-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]carbamate (C27)

A vial was charged with tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (50 mg, 0.11 mmol), tris(p-methoxyphenyl)bismuth diacetate (106 mg, 0.163 mmol), toluene (544 μl) and diacetoxycopper (2.0 mg, 11 μmol). N-cyclohexyl-N-methylcyclohexanamine (46.2 μl, 0.218 mmol) was added and the reaction was heated to 50° C. and stirred overnight. The heterogeneous mixture was filtered through a plug of Celite®, the filtrate concentrated, and the residue purified by automated flash chromatography (0→50% EtOAc/hexanes) to afford a colorless semi-solid (43 mg, 69%): ¹H NMR (400 MHz, CDCl₃) δ 7.01 (d, J=9.1 Hz, 2H), 6.79 (d, J=9.1 Hz, 2H), 4.96-4.72 (m, 2H), 4.23 (dd, J=9.6, 7.3 Hz, 1H), 3.76 (s, 3H), 3.51 (ddd, J=7.1, 5.1, 1.8 Hz, 1H), 3.24 (dd, J=8.8, 6.7 Hz, 1H), 3.08 (dd, J=8.8, 6.2 Hz, 1H), 2.44-2.33 (m, 1H), 2.18 (dddd, J=15.5, 10.0, 8.1, 5.1 Hz, 1H), 2.05 (dddd, J=13.6, 8.2, 6.3, 1.7 Hz, 1H), 1.83-1.64 (m, 3H), 1.52 (s, 18H), 1.34 (d, J=6.3 Hz, 3H), 1.03 (ddt, J=15.8, 7.6, 1.9 Hz, 1H), 0.79 (dd, J=18.5, 6.7 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.85, 154.09, 154.02, 152.86, 117.55, 114.37, 83.88, 83.14, 82.73, 76.36, 72.80, 57.40, 55.68, 30.57, 28.73, 28.38, 27.98, 19.43, 19.29, 19.21, 18.28; IR (thin film) 2977, 1744, 1704, 1506, 1140 cm⁻¹; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₃₀H₄₇NNaO₉, 588.3143; found, 588.3146.

Example 13B, Step 3 Preparation of [(3S,7S,8S,9S)-7-isobutoxy-8-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F7)

Prepared according to the methods described in Example 12A.

Example 13C, Step 1 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-8-(2-methylallyloxy)-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (An alternate method to prepare C16)

A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-8-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (56.0 mg, 0.122 mmol), triphenylbismuth diacetate (137 mg, 0.245 mmol) and diacetoxycopper (4.4 mg, 0.024 mmol) in toluene (1224 μl) was stirred at 40° C. overnight. The reaction mixture was filtered thru Celite®, the pad washed with toluene (2×10 mL), and the filtrate concentrated to yield a light blue foam. Purification by column chromatography (SiO₂; 0→20% EtOAc/hexanes) afforded the title compound (45 mg, 69%) as a white solid: See Compound 16 (Example 12B, Step 1) for analytical data.

Example 13C, Step 2 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (An alternate method to prepare C18)

Prepared according to the procedure described for example 12B step 2 and isolated as a clear oil (430 mg; 100%): ¹H NMR (400 MHz, CDCl₃) δ 7.32-7.22 (m, 2H), 6.99-6.86 (m, 3H), 4.86 (dd, J=10.2, 8.2 Hz, 1H), 4.75 (dq, J=9.7, 6.3 Hz, 1H), 4.43-4.26 (m, 1H), 3.66-3.50 (m, 2H), 3.36 (dd, J=8.7, 6.7 Hz, 1H), 2.44-2.24 (m, 1H), 2.24-2.08 (m, 1H), 2.04-1.91 (m, 1H), 1.89-1.56 (m, 3H), 1.53-1.46 (m, 18H), 1.44 (d, J=6.3 Hz, 3H), 1.06 (dd, J=16.0, 7.9 Hz, 1H), 0.82 (d, J=6.7 Hz, 3H), 0.78 (d, J=6.7 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.78, 157.65, 152.86, 129.44, 121.06, 116.54, 83.33, 83.06, 82.71, 80.56, 72.93, 57.27, 30.46, 28.97, 28.85, 27.97, 19.39, 19.28, 19.17, 18.15; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₉H₄₅NNaO₈, 558.3037; found, 558.2994.

Example 13C, Step 3 Preparation of [(3S,7S,8S,9S)-8-isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]ammonium chloride (An alternative route to prepare F4)

Prepared according to the methods described in Example 12B, Step 3.

Example 13D, Step 1 Preparation of [(2S,3S,4S,8S)-8-[bis(tert-butoxycarbonyl)amino]-3-isobutoxy-2-methyl-9-oxo-oxonan-4-yl]cyclopentanecarboxylate (C28)

To a 10 mL screw-cap vial were added tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-8-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (200 mg, 0.44 mmol), pyridine (105 μl, 1.31 mmol) and CH₂Cl₂ (2176 μl), followed by cyclopentanecarbonyl chloride (79 μl, 0.65 mmol). The vial was sealed under N₂ and the reaction was magnetically stirred overnight. The crude mixture was purified by column chromatography (SiO₂, 1→25% acetone/hexanes) to yield the title compound (203 mg, 84%): ¹H NMR (400 MHz, CDCl₃) δ 4.92 (ddd, J=7.4, 5.3, 1.9 Hz, 1H), 4.85 (dd, J=10.3, 8.0 Hz, 1H), 4.72 (dq, J=9.7, 6.3 Hz, 1H), 3.45 (dd, J=9.6, 7.6 Hz, 1H), 3.39-3.28 (m, 2H), 2.72 (p, J=7.9 Hz, 1H), 2.40-2.26 (m, 1H), 2.17-1.95 (m, 2H), 1.92-1.69 (m, 8H), 1.58 (ddd, J=10.7, 5.5, 3.0 Hz, 3H), 1.51 (s, 18H), 1.41 (d, J=6.3 Hz, 3H), 1.12-1.00 (m, 1H), 0.86 (t, J=7.0 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 175.65, 170.57, 152.78, 82.78, 82.17, 80.05, 77.85, 72.95, 57.22, 44.14, 30.53, 30.22, 29.75, 29.58, 28.99, 27.97, 25.79, 19.36, 19.28, 18.04; ESIMS m/z 578.4 [(M+Na)⁺].

The following compounds were prepared and isolated using the methodology described in Example 13D, Step 1:

[(2S,3S,4S,8S)-8-[bis(tert-butoxycarbonyl)amino]-4-isobutoxy-2-methyl-9-oxo-oxonan-3-yl]cyclopentanecarboxylate (C29)

Isolated as a white solid (98%): mp 101-106° C.; ¹H NMR (400 MHz, CDCl₃) δ 5.12 (dd, J=9.7, 7.8 Hz, 1H), 4.88-4.73 (m, 2H), 3.36 (ddd, J=7.5, 5.2, 2.0 Hz, 1H), 3.26 (dd, J=8.7, 6.3 Hz, 1H), 2.97 (dd, J=8.7, 6.6 Hz, 1H), 2.72 (p, J=7.9 Hz, 1H), 2.36 (tdd, J=12.5, 10.3, 1.9 Hz, 1H), 2.22-1.98 (m, 2H), 1.95-1.55 (m, 10H), 1.51 (s, 18H), 1.26 (d, J=6.4 Hz, 3H), 1.02 (ddt, J=15.7, 7.3, 2.0 Hz, 1H), 0.84 (d, J=6.7 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 175.60, 170.93, 152.83, 82.71, 81.23, 76.10, 75.21, 71.65, 57.37, 43.98, 30.58, 30.13, 29.74, 28.69, 28.36, 27.97, 25.81, 25.70, 19.38, 19.34, 18.96, 17.38; ESIMS m/z 578.5 ([M+Na]⁺).

Example 13D, Step 2 Preparation of [(3S,7S,8S,9S)-7-(cyclopentanecarbonyloxy)-8-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F8)

Prepared according to the methods described in Example 12A.

The following compounds were prepared and isolated using the methodology described in Example 13D, Step 2:

[(3S,7S,8S,9S)-8-(cyclopentanecarbonyloxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F9)

Example 13E, Step 1 Preparation of (2S,3S,4S,8S)-8-((bis tert-butoxycarbonyl)amino)-2-methyl-4-((2-methylallyl)oxy)-9-oxooxonan-3-yl cyclopropanecarboxylate (C30)

To a solution tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (500 mg, 1.09 mmol) in CH₂Cl₂ (2.2 mL) was added pyridine (0.265 mL, 3.28 mmol) and cyclopropanecarbonyl chloride (0.149 mL, 1.64 mmol). The resulting solution was stirred at room temperature for 16 h, then purified by automated silica gel column chromatography (0→100% EtOAc/hexanes) to provide a light yellow solid (599 mg, 99%): IR (thin film) 2979, 2938, 1737, 1703, 1355, 1159 cm⁻; ¹H NMR (400 MHz, CDCl₃) δ 5.14 (dd, J=9.7, 7.8 Hz, 1H), 4.95-4.66 (m, 4H), 3.94 (d, J=12.3 Hz, 1H), 3.76 (d, J=12.2 Hz, 1H), 3.46 (ddd, J=7.6, 5.3, 1.9 Hz, 1H), 2.37 (q, J=11.9, 11.3 Hz, 1H), 2.21-2.00 (m, 2H), 1.87-1.74 (m, 1H) 1.71 (s, 3H), 1.51 (s, 18H), 1.28 (d, J=6.3 Hz, 3H), 1.17 (dt, J=6.9, 4.2 Hz, 1H), 1.11-0.97 (m, 4H), 0.87 (dq, J=6.4, 3.7 Hz, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 173.98, 170.89, 152.84, 142.11, 112.39, 82.73, 80.01, 75.46, 73.07, 71.66, 57.36, 30.57, 28.55, 27.97, 19.41, 19.03, 17.36, 12.89, 10.18, 8.49, 8.43.

Example 13E, Step 2 Preparation of (2S,3S,4S,8S)-8-((bis tert-butoxycarbonyl)amino)-4-isobutoxy-2-methyl-9-oxooxonan-3-yl cyclopropanecarboxylate (C31)

Prepared according to the methodology described in Example 13B, Step 1 to give the title compound (424 mg, 89%) as a white solid: IR (thin film) 2978, 1739, 1706, 1162 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 5.11 (dd, J=9.7, 7.8 Hz, 1H), 4.88-4.70 (m, 2H), 3.36 (ddd, J=7.6, 5.2, 2.0 Hz, 1H), 3.30 (dd, J=8.8, 6.1 Hz, 1H), 2.98 (dd, J=8.8, 6.8 Hz, 1H), 2.36 (dddd, J=13.9, 12.1, 10.1, 1.8 Hz, 1H), 2.22-1.97 (m, 2H), 1.85-1.69 (m, 2H), 1.70-1.55 (m, 2H), 1.51 (s, 18H), 1.27 (d, J=6.4 Hz, 3H), 1.12-0.96 (m, 3H), 0.91-0.82 (m, 8H); ¹³C NMR (101 MHz, CDCl₃) δ 173.94, 170.92, 152.84, 82.72, 81.25, 76.30, 75.50, 71.65, 57.37, 30.61, 28.63, 27.97, 19.32, 19.27, 19.00, 17.35, 12.89, 8.43, 8.36; HRMS-ESI (m/z) [M+H]⁺ calcd for C₂H₄₆NO₉, 528.3167; found, 528.3167.

Example 13E, Step 3 Preparation of [(3S,7S,8S,9S)-8-(cyclopropanecarbonyloxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F10)

Prepared according to the methods described in Example 12A.

Example 13F, Step 1 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[(E)-4,4,4-trifluorobut-2-enoxy]oxonan-3-yl]carbamate (C32)

A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (499 mg, 1.09 mmol), (E)-bis tert-butyl (4,4,4-trifluorobut-2-en-1-yl) carbonate (493 mg, 2.18 mmol), dppf (60.5 mg, 0.109 mmol) and Pd₂(dba)₃ (49.9 mg, 0.055 mmol) in degassed THF (5453 μl) was heated to 60° C. for 1.5 h. The solution was cooled to room temperature and purified by automated flash chromatography (SiO2; 0→10% EtOAc/hexanes) to yield the title compound as a yellow semi-solid (292 mg, 73%): ¹H NMR (400 MHz, CDCl₃) δ 6.44-6.36 (m, 1H), 5.96-5.78 (m, 1H), 4.96-4.92 (m, 1H), 4.88-4.85 (m, 1H), 4.82 (dd, J=10.3, 8.0 Hz, 1H), 4.73-4.64 (m, 1H), 4.46 (m, 1H), 4.30-4.21 (m, 1H), 3.96 (d, J=12.1 Hz, 1H), 3.79 (d, J=12.1 Hz, 1H), 3.50-3.39 (m, 2H), 2.36 (dd, J=12.0, 2.6 Hz, 1H), 2.19-1.98 (m, 2H), 1.72 (s, 3H), 1.70-1.59 (m, 2H), 1.51 (s, 18H), 1.38 (d, J=6.3 Hz, 3H), 0.97 (dd, J=16.3, 7.7 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.79, 152.89, 142.25, 136.73, 118.34, 118.01, 112.25, 84.21, 83.30, 82.74, 77.21, 72.89, 72.49, 71.03, 57.31, 30.50, 28.23, 27.98, 19.59, 19.18, 18.04; ESIMS m/z 588.3 ([M+Na]⁺).

Example 13F, Step 2 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl]carbamate (C33)

The tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[(E)-4,4,4-trifluorobut-2-enoxy]oxonan-3-yl]carbamate (451 mg, 0.80 mmol) was dissolved in EtOAc (4 mL) in a vial and Pd/C (5% w/w Pd, 85 mg, 0.040 mmol) was added. The vial was evacuated and backfilled with hydrogen (1 atm), then stirred vigorously at room temperature. After stirring for 16 h, the reaction mixture was filtered through a pad of Celite® and concentrated to provide a white solid (454 mg, 100%) ¹H NMR (400 MHz, CDCl₃) δ 4.80 (dd, J=10.4, 8.0 Hz, 1H), 4.62 (pd, J=6.2, 2.0 Hz, 1H), 3.83 (dt, J=9.3, 6.0 Hz, 1H), 3.64 (dt, J=9.3, 6.1 Hz, 1H), 3.40-3.20 (m, 3H), 3.08 (dd, J=8.7, 6.2 Hz, 1H), 2.45-2.28 (m, 1H), 2.25-2.04 (m, 2H), 2.07-1.95 (m, 1H), 1.88-1.73 (m, 3H), 1.73-1.57 (m, 3H), 1.51 (s, 18H), 1.36 (d, J=6.4 Hz, 3H), 0.95-0.83 (m, 7H); ¹⁹F NMR (376 MHz, CDCl₃) δ −66.43; ¹³C NMR (101 MHz, CDCl₃) δ 170.88, 152.89, 84.07, 83.91, 82.70, 75.65, 72.75, 71.58, 57.39, 31.05, 30.76, 30.50, 28.88, 27.97, 23.07, 23.05, 19.55, 19.47, 19.11, 18.09; ESIMS m/z 592.3 ([M+Na]⁺).

Example 13F, Step 3 Preparation of [(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl]ammonium chloride (F11)

Prepared according to the methods described in Example 12A.

Example 13G, Step 1 Preparation of tert-butyl N-[(3S,7S,8S,9S)-7-allyloxy-8-cyclopent-2-en-1-yloxy-9-methyl-2-oxo-oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate (C34)

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-cyclopent-2-en-1-yloxy-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (200 mg, 0.43 mmol), Pd₂(dba)₃ (39.0 mg, 0.043 mmol) and dppf (47.2 mg, 0.085 mmol) in THF (2.1 mL) at room temperature was added allyl tert-butyl carbonate (202 mg, 1.28 mmol). The reaction was stirred at 60° C. overnight. The reaction mixture was concentrated and purified by column chromatography on SiO₂ (5→25% EtOAc/hexanes) to yield the title compound as a yellow oil (160 mg, 74%): IR (thin film) 2978, 2933, 1742, 1703; ¹H NMR (400 MHz, CDCl₃) δ 6.05-5.84 (m, 3H), 5.30-5.24 (m, 1H), 5.17-5.13 (m, 1H), 4.93-4.76 (m, 2H), 4.68-4.53 (m, 1H), 4.13-4.05 (m, 1H), 3.98-3.92 (m, 1H), 3.54-3.50 (m, 1H), 3.45-3.38 (m, 1H), 2.52-2.29 (m, 2H), 2.28-1.89 (m, 4H), 1.81-1.57 (m, 3H), 1.51 (s, 18H), 1.39 (d, J=6.4 Hz, 3H), 1.00-0.88 (m, 1H); ESIMS m/z 532.4 ([M+Na]⁺).

Example 13G, Step 2 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-(cyclopentoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]carbamate (C35)

Prepared according to the methodology described in Example 13F, Step 2 to give the title compound (286 mg, 95%) as a colorless oil): ¹H NMR (400 MHz, CDCl₃) δ 4.79 (dd, J=10.6, 7.9 Hz, 1H), 4.57 (dq, J=9.5, 6.4 Hz, 1H), 4.32-4.25 (m, 1H), 3.53-3.37 (m, 2H), 3.35-3.27 (m, 2H), 2.42-2.28 (m, 1H), 2.19-1.95 (m, 2H), 1.83-1.53 (m, 12H), 1.51 (s, 18H), 1.37 (d, J=6.4 Hz, 3H), 0.92 (t, J=7.4 Hz, 3H), 0.90-0.87 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.93, 152.86, 84.28, 83.25, 82.60, 81.26, 73.34, 70.89, 57.47, 32.91, 32.35, 30.50, 28.36, 27.94, 23.33, 23.23, 23.19, 19.20, 18.20, 10.76; ESIMS m/z 536.5 ([M+Na]⁺).

Example 13G, Step 3 Preparation of [(3S,7S,8S,9S)-8-(cyclopentoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]ammonium chloride (F11)

Prepared according to the methods described in Example 12A.

Example 14 Preparation of (2S,3S,4S,8S)-8-((bis tert-butoxycarbonyl)amino)-2-methyl-9-oxooxonane-3,4-diyl dicyclopentanecarboxylate (C36)

A 20 mL vial was charged with tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (300 mg, 0.74 mmol), CH₂Cl₂ (3.7 mL), and DMAP (182 mg, 1.49 mmol). Cyclopentanecarbonyl chloride (181 μL, 1.49 mmol) was added dropwise to the colorless solution, which then became dark brown. The reaction flask was placed in a room temperature water bath. The reaction mixture was stirred overnight, concentrated, and partially purified using automated flash chromatography (SiO₂; 0→100% EtOAc/hexanes) to give fractions that all contained an impurity derived from the cyclopentanecarbonyl chloride. The impure fractions were combined, washed with 1N HCl, then saturated NaHCO₃ and brine, and then concentrated to give a colorless oil (80.2 mg, 18%): IR (thin film) 2954, 1741, 1706, 1140 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 5.24 (dd, J=9.9, 8.1 Hz, 1H), 5.00 (ddd, J=7.8, 5.2, 2.2 Hz, 1H), 4.92-4.81 (m, 2H), 2.83-2.72 (m, 2H), 2.36 (dddd, J=13.8, 12.1, 10.1, 1.8 Hz, 1H), 2.19-2.00 (m, 2H), 1.98-1.78 (m, 5H), 1.78-1.54 (m, 13H), 1.51 (s, 18H), 1.28 (d, J=6.3 Hz, 3H), 1.19 (ddt, J=16.2, 7.8, 2.2 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 175.75, 175.55, 170.61, 152.75, 99.98, 82.86, 74.97, 73.67, 71.33, 57.12, 43.91, 43.80, 30.46, 30.07, 29.98, 29.93, 29.79, 29.62, 27.96, 25.76, 25.69, 19.08, 17.35; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₃₁H₄₉NNaO₁₀, 618.3249; found, 618.3250.

Example 14A Preparation of [(3S,7S,8S,9S)-7,8-bis(cyclopentanecarbonyloxy)-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F12)

Prepared according to the methods described in Example 12A.

Example 15, Step 1 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[3-oxobut-1-enoxy]oxonan-3-yl]carbamate (C37)

To a 100 mL round bottomed flask were charged tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (800 mg, 1.75 mmol), DABCO (9.8 mg, 0.087 mmol) and CH₂Cl₂ (8742 μl). The colorless solution was cooled to 0° C., then but-3-yn-2-one (163 μl, 2.10 mmol) was added dropwise over 10 min. The solution became dark brown. After stirring for 2 h, the reaction mixture was concentrated and purified by automated flash chromatography (SiO₂; 0→100% EtOAc/hexanes) to afford a white solid as an approximate 4:1 mixture of E/Z isomers (0.953 g, 100%): IR (thin film) 2976, 2937, 1742, 1727, 1632, 1139, 1119 cm⁻¹; ¹H NMR (Major isomer; 400 MHz, CDCl₃) δ 7.50 (d, J=12.3 Hz, 1H), 5.67 (d, J=12.4 Hz, 1H), 4.95-4.76 (m, 4H), 3.94-3.86 (m, 2H), 3.76 (d, J=11.9 Hz, 1H), 3.46 (ddd, J=7.3, 4.9, 1.9 Hz, 1H), 2.49-2.32 (m, 1H), 2.21-2.11 (m, 1H), 2.16 (s, 3H), 2.10-2.01 (m, 1H), 1.75-1.64 (m, 5H), 1.52 (s, 18H), 1.35 (d, J=6.4 Hz, 3H), 1.07-0.96 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 197.43, 170.60, 164.05, 152.85, 141.82, 112.84, 108.78, 87.97, 82.88, 81.36, 73.01, 71.03, 57.12, 30.41, 27.97, 27.80, 27.50, 19.59, 19.07, 17.96; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₇H₄₃NNaO₉, 548.2830; found, 548.2826.

Example 15, Step 2 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl]carbamate (C38)

A round bottomed flask was charged with tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[3-oxobut-1-enoxy]oxonan-3-yl]carbamate (954 mg, 1.82 mmol), Pd/C (5% w/w Pd, 193 mg, 0.091 mmol), and EtOAc (9 mL). The flask was evacuated and backfilled with N₂, then evacuated and backfilled with H₂. The reaction mixture was stirred vigorously at room temperature overnight. The crude reaction mixture was filtered through a plug of Celite® and the filtrate concentrated to give a crude solid. The solid was purified by automated flash chromatography (SiO₂; 0→100% EtOAc/hexanes) to give a white solid (785 mg, 82%): IR (thin film) 2977, 2937, 1743, 1704, 1356, 1141 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 4.80 (dd, J=10.5, 8.0 Hz, 1H), 4.65-4.53 (m, 1H), 4.02 (dt, J=9.5, 6.0 Hz, 1H), 3.89 (ddd, J=9.5, 7.1, 5.7 Hz, 1H), 3.36-3.23 (m, 3H), 3.11 (dd, J=8.8, 6.2 Hz, 1H), 2.74-2.56 (m, 2H), 2.41-2.26 (m, 1H), 2.17 (s, 3H), 2.15-2.06 (m, 1H), 2.03-1.96 (m, 1H), 1.87-1.76 (m, 1H), 1.73-1.60 (m, 2H), 1.51 (d, J=2.4 Hz, 18H), 1.35 (d, J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 1.4 Hz, 6H), 0.87 (dd, J=7.1, 1.9 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 207.19, 170.86, 152.87, 84.02, 83.99, 82.67, 75.65, 72.76, 68.23, 57.39, 44.20, 30.49, 28.89, 28.06, 27.97, 19.56, 19.49, 19.13, 18.02; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₇H₄₇NNaO₉, 552.3143; found, 552.3158.

Example 15, Step 3 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-8-(3-methoxybutoxy)-9-methyl-2-oxo-oxonan-3-yl]carbamate (C39)

The tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl]carbamate (400 mg, 0.76 mmol) was dissolved in MeOH (3.8 mL) and cooled to 0° C. under N₂, and NaBH₄ (5 mg, 1.72 mmol) was added in one portion. The reaction was stirred for 2.5 h and then quenched by the addition of saturated aqueous NH₄Cl solution. The mixture was extracted with EtOAc, and the extracts were washed with brine, dried over Na₂SO₄, filtered, and concentrated to afford tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-(3-hydroxybutoxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (382 mg, 95%) as a colorless oil, which was used without further purification. An oven-dried round bottom flask was charged with the diastereomeric mixture of the alcohol (405 mg, 0.762 mmol), Proton Sponge® (653 mg, 3.05 mmol), and CH₂Cl₂ (5 mL). Trimethyloxonium tetrafluoroborate (225 mg, 1.52 mmol) was added in one portion to the colorless solution. A white suspension formed, and the mixture was stirred at room temperature. After stirring for 6 h, the reaction was quenched by the addition of saturated aqueous NaHCO₃ (3 mL) and the phases were separated. The aqueous layer was extracted with CH₂Cl₂ and the combined organic layers were washed with brine, passed through a phase separator cartridge, concentrated, and purified by automated flash chromatography (SiO₂; 0→100% EtOAc/hexanes) to afford a light pink oil as a mixture of diastereomers (328 mg, 79%): IR (thin film) 2935, 1745, 1706, 1142 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 4.91-4.75 (m, 1H), 4.71-4.51 (m, 1H), 4.02-3.93 (m, 1H), 3.91-3.78 (m, 1H), 3.74-3.59 (m, 1H), 3.50-3.36 (m, 1H), 3.36-3.31 (m, 2H), 3.30 (s, 2H), 3.29-3.22 (m, 1H), 3.13 (tt, J=8.7, 6.1 Hz, 1H), 2.43-2.27 (m, 1H), 2.18-1.92 (m, 2H), 1.90-1.75 (m, 1H), 1.75-1.59 (m, 4H), 1.51 (s, 18H), 1.43-1.33 (m, 3H), 1.18 (dd, J=6.2, 2.9 Hz, 1H), 1.14-1.12 (m, 2H), 0.96-0.85 (m, 7H); ¹³C NMR (101 MHz, CDCl₃) δ 170.92, 170.90, 152.89, 85.49, 84.82, 84.27, 84.14, 83.71, 82.68, 82.66, 82.61, 76.35, 75.95, 75.91, 75.53, 73.48, 73.11, 72.87, 61.27, 58.72, 57.44, 57.40, 56.51, 36.20, 32.47, 30.57, 30.54, 29.01, 28.87, 28.84, 28.29, 28.24, 19.63, 19.54, 19.49, 19.37, 19.15, 18.02, 17.92, 17.72, 15.73, 13.96; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₈H₅₁NNaO₉, 568.3456; found, 568.3453.

Example 15, Step 4 Preparation of [(3S,7S,8S,9S)-8-(3-methoxybutoxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F13)

Prepared using the methodology described in Example 12A.

Example 16A Preparation of 3-hydroxy-4-methoxy-N-((3S,7S,8S,9S)-9-methyl-7,8-bis((2-methylallyl)oxy)-2-oxooxonan-3-yl)pyridine-2-carboxamide (F14)

To a suspension of the [(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]ammonium chloride (256 mg, 0.736 mmol) and 3-hydroxy-4-methoxypicolinic acid (137 mg, 0.809 mmol) in CH₂Cl₂ (6.0 ml) was added Hünig's base (0.422 ml, 2.42 mmol) followed by PyBOP (421 mg, 0.809 mmol). The reaction was stirred at room temperature for 90 min. The solvent was then removed and the resulting crude residue was purified by automated silica gel column chromatography (1→66% acetone/hexanes) to afford the title compound (246 mg, 72%) as a white foam.

Example 16B Preparation of N-[(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]-3-hydroxy-4-methoxypyridine-2-carboxamide (F15)

To a suspension of the [(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (220 mg, 0.52 mmol) and 3-hydroxy-4-methoxypicolinic acid (124 mg, 0.733 mmol) in CH₂Cl₂ (5.2 mL) was added N-methylmorpholine (0.346 mL, 3.14 mmol) followed by HATU (299 mg, 0.786 mmol). The mixture was stirred at room temperature for 5 h, then the solvent was removed and the crude residue was purified by automated silica gel column chromatography (5→20% acetone/hexanes) to afford the title compound (124 mg, 44.3%) as a hard white foam.

Example 17A Preparation of [4-methoxy-2-[[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamoyl]-3-pyridyl]oxymethyl acetate (F16)

To a screw-cap vial were added 3-hydroxy-4-methoxy-N-((3S,7S,8S,9S)-9-methyl-7,8-bis((2-methylallyl)oxy)-2-oxooxonan-3-yl)pyridine-2-carboxamide (110 mg, 0.24 mmol) and K₂CO₃ (65.7 mg, 0.476 mmol), followed by acetone (2.38 ml). Then, bromomethyl acetate (33 μL, 0.34 mmol) was added dropwise and the reaction was heated to 50° C. for 1 h. The reaction mixture was cooled to room temperature, filtered through a plug of glass wool, and then the solvent was removed. The crude residue was purified by automated silica gel column chromatography (1-50% acetone/hexanes) to afford the title compound (98.9 mg, 78%) as a colorless oil.

Example 17B Preparation of [4-methoxy-2-[[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamoyl]-3-pyridyl]oxymethyl-2-methylpropanoate (F17)

To a screw-cap vial were added 3-hydroxy-4-methoxy-N-((3S,7S,8S,9S)-9-methyl-7,8-bis((2-methylallyl)oxy)-2-oxooxonan-3-yl)pyridine-2-carboxamide (110 mg, 0.24 mmol), powdered Na₂CO₃ (50.4 mg, 0.476 mmol), and NaI (5.4 mg, 0.036 mmol) followed by acetone (2.38 ml). Then, chloromethyl isobutyrate (0.042 ml, 0.33 mmol) was added dropwise and the reaction was heated to 50° C. for 14 h. The reaction mixture was cooled to room temperature, filtered through a plug of glass wool, and then the solvent was evaporated. The crude residue was purified by automated silica gel column chromatography (1→50% acetone/hexanes) to afford the title compound (127.9 mg, 96%) as a colorless oil.

Example 17C Preparation of [2-[[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]acetate (F18)

To a screw-cap vial were added 3-hydroxy-N-[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]-4-methoxypyridine-2-carboxamide (17.0 mg, 0.037 mmol) and CH₂Cl₂ (0.52 mL), followed by DMAP (0.89 mg, 0.73 μmol) and TEA (10.2 μl, 0.073 mmol). Then, acetyl chloride (3.9 μl, 0.055 mmol) was added and the reaction was stirred at room temperature for 3 h. The mixture was diluted with CH₂Cl₂ and quenched by pouring into saturated aqueous NH₄Cl. The organic phase was separated and the aqueous phase was extracted with CH₂Cl₂ three times. The combined organic phases were passed through a phase separator and the solvent was then evaporated. The resulting crude residue was purified by automated silica gel column chromatography (1→50% acetone/hexanes) to afford the title compound (15.7 mg, 85%) as a colorless oil.

Example 17D Preparation of [2-[[(3S,7S,8S,9S)-7-(cyclopentoxy)-9-methyl-2-oxo-8-propoxy-oxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]3-methoxypropanoate (F19)

To a screw-cap vial were added N-[(3S,7S,8S,9S)-7-(cyclopentoxy)-9-methyl-2-oxo-8-propoxy-oxonan-3-yl]-3-hydroxy-4-methoxypyridine-2-carboxamide (51.7 mg, 0.111 mmol) and CH₂Cl₂ (1.1 mL), followed by DMAP (6.8 mg, 0.056 mmol) and TEA (30.9 μl, 0.223 mmol). Then, 3-methoxypropanoyl chloride (24.1 μl, 0.223 mmol) was added dropwise and the reaction was stirred at room temperature for 3 h. The mixture was diluted with CH₂Cl₂ and quenched by pouring into saturated aqueous NH₄Cl. The organic phase was separated and the aqueous phase was extracted with CH₂Cl₂ three times. The combined organic phases were passed through a phase separator and the solvent was then evaporated. The resulting crude residue was purified by automated silica gel column chromatography (1→50% acetone/hexanes) to afford the title compound (58.7 mg, 96%) as a white solid.

Example 18 Preparation of tert-butyl ((3aS,4S,7S,10aS)-4-methyl-6-oxo-2-phenyloctahydro-[1,3]dioxolo[4,5-c]oxonin-7-yl)carbamate

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (250 mg, 0.620 mmol) in CH₂Cl₂ (3 mL) were added 4-methylbenzenesulfonic acid (21.34 mg, 0.124 mmol), benzaldehyde (315 μl, 3.10 mmol), and MgSO₄ (100 mg), and the reaction was stirred at ambient temperature for 2 h. The reaction mixture was filtered through a plug of Celite®, concentrated and purified via silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (240 mg, 99%) as a white solid: ¹H NMR (400 MHz, CDCl₃) δ 7.47 (tdd, J=5.2, 4.2, 2.8 Hz, 2H), 7.38 (dp, J=5.7, 1.5 Hz, 3H), 5.79 (s, 1H), 5.31-5.15 (m, 2H), 4.17 (ddd, J=12.4, 7.9, 5.0 Hz, 1H), 3.90 (ddd, J=11.4, 6.9, 3.0 Hz, 1H), 3.68 (dd, J=9.7, 6.9 Hz, 1H), 2.30 (ddd, J=17.7, 10.1, 4.5 Hz, 1H), 2.10-1.89 (m, 2H), 1.84-1.57 (m, 2H), 1.49 (d, J=6.3 Hz, 3H), 1.45 (s, 9H), 1.43-1.31 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.75, 154.81, 136.32, 129.69, 128.44, 126.79, 102.84, 83.62, 80.04, 79.70, 71.69, 54.23, 34.42, 32.94, 30.94, 28.33, 19.76, 18.33; ESIMS m/z 414 ([M+H]⁺).

Example 19 Preparation of tert-butyl N-[(3aS,4S,7S,10aS)-2-ethyl-4-methyl-6-oxo-4,7,8,9,10,10a-hexahydro-3aH-[1,3]dioxolo[4,5-c]oxonin-7-yl]-N-tert-butoxycarbonyl-carbamate

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (250 mg, 0.620 mmol) in CH₂Cl₂ (3.1 mL) were added 4-methylbenzenesulfonic acid (21.34 mg, 0.124 mmol), propionaldehyde (225 μl, 3.10 mmol), and MgSO₄ (100 mg), and the reaction was stirred at ambient temperature for 2 h. The reaction mixture was filtered through a plug of Celite®, concentrated and purified via silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (217 mg, 79%) as a sticky, colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 4.93 (dq, J=9.6, 6.3 Hz, 1H), 4.83 (t, J=4.6 Hz, 1H), 4.67 (dd, J=12.3, 4.8 Hz, 1H), 3.69 (ddd, J=11.3, 6.8, 2.7 Hz, 1H), 3.47 (dd, J=9.6, 6.9 Hz, 1H), 2.39 (dddd, J=13.9, 12.2, 6.6, 1.6 Hz, 1H), 2.16-1.91 (m, 3H), 1.80-1.59 (m, 4H), 1.51 (s, 18H), 1.43 (d, J=6.2 Hz, 3H), 0.94 (t, J=7.6 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 171.36, 152.87, 104.15, 83.14, 82.76, 79.54, 72.13, 59.10, 34.45, 30.54, 27.97, 26.41, 21.04, 18.53, 7.93; ESIMS m/z 444 ([M+H]⁺).

Example 20 Preparation of A) tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-(3-fluorophenoxy)-8-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate and B) tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-(3-fluorophenoxy)-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate

To a solution of tris(3-fluorophenyl)bismuthine (1.056 g, 2.137 mmol) in CH₂Cl₂ (7.12 mL) was added peracetic acid (0.503 mL, 2.421 mmol) at 0° C., and the solution was warmed to room temperature and stirred for 20 min. To the resulting solution were added tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (575 mg, 1.42 mmol) and diacetoxycopper (52 mg, 0.28 mmol), and the resulting blue-green slurry was stirred at room temperature for 16 h, warmed to 40° C., and stirred at 40° C. for 4 h. The reaction mixture was filtered through a plug of Celite and any peroxides in the filtrate were quenched by the addition of saturated aqueous sodium bisulfite (NaHSO₃). The biphasic mixture was passed through a phase separator cartridge and concentrated. The crude residue was purified by silica gel chromatography (gradient, petroleum ether/MTBE) to afford the title compounds A and B.

Compound A (117 mg, 16%) was isolated as a light yellow oil: ¹H NMR (400 MHz, CDCl₃) δ 7.22 (td, J=8.2, 6.8 Hz, 1H), 6.74-6.61 (m, 3H), 4.95 (t, J=8.5 Hz, 1H), 4.84 (dq, J=9.5, 6.2 Hz, 1H), 4.17 (ddd, J=7.8, 6.0, 1.9 Hz, 1H), 3.86 (ddd, J=9.6, 7.6, 2.3 Hz, 1H), 2.64 (d, J=2.7 Hz, 1H), 2.29 (dddd, J=14.0, 11.2, 8.6, 1.7 Hz, 1H), 2.35-2.24 (m, 1H), 2.13-1.99 (m, 2H), 1.89 (dddd, J=17.3, 15.9, 8.6, 3.9 Hz, 1H), 1.68-1.55 (m, 1H), 1.52 (s, 18H), 1.47 (d, J=6.3 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −111.22; ESIMS m/z 498 ([M+H]⁺).

Compound B (214 mg, 30%) was isolated as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 7.23 (td, J=8.3, 6.7 Hz, 1H), 6.83 (ddd, J=8.4, 2.5, 0.9 Hz, 1H), 6.77 (dt, J=10.8, 2.4 Hz, 1H), 6.70 (dddd, J=8.3, 7.4, 2.4, 1.2 Hz, 1H), 4.95-4.83 (m, 2H), 4.27 (dd, J=9.5, 7.8 Hz, 1H), 3.88 (ddt, J=8.1, 5.3, 2.3 Hz, 1H), 2.45-2.33 (m, 1H), 2.16-2.13 (m, 1H), 2.13-1.97 (m, 2H), 1.83 (dtd, J=12.2, 9.4, 8.2, 6.1 Hz, 2H), 1.52 (s, 18H), 1.49-1.39 (m, 1H), 1.32 (d, J=6.4 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −110.94; ESIMS m/z 498 ([M+H]⁺).

Example 21 Preparation of tert-butyl N-[(3S,7S,8S,9S)-8-(4-bromophenoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-8-phenoxy-7-propoxy-oxonan-3-yl]carbamate (523 mg, 1.003 mmol) in CH₂Cl₂ (5 mL) was added NBS (357 mg, 2.005 mmol). The vial was wrapped in aluminum foil and stirred at room temperature for 16 h. An additional portion of NBS (357 mg, 2 mmol) was added and the reaction was stirred at room temperature for an additional 3 h, concentrated, and the residue purified by silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (567 mg, 94%): ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.30 (m, 2H), 7.00-6.91 (m, 2H), 4.90-4.78 (m, 2H), 4.28 (dd, J=9.7, 7.3 Hz, 1H), 3.52 (ddd, J=7.2, 5.2, 1.9 Hz, 1H), 3.44 (dt, J=9.0, 6.6 Hz, 1H), 3.20 (dt, J=9.0, 6.5 Hz, 1H), 2.48-2.33 (m, 1H), 2.23-2.11 (m, 1H), 2.12-2.00 (m, 1H), 1.82-1.65 (m, 2H), 1.52 (s, 18H), 1.47-1.36 (m, 2H), 1.31 (d, J=6.4 Hz, 3H), 1.12-0.99 (m, 1H), 0.77 (t, J=7.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.80, 158.94, 152.87, 132.12, 118.28, 113.38, 83.31, 82.96, 82.76, 72.40, 71.28, 57.34, 30.53, 27.98, 23.15, 19.23, 18.17, 10.56; ESIMS m/z 622 ([M+H]⁺).

Example 22 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-8-(4-phenylphenoxy)-7-propoxy-oxonan-3-yl]carbamate

A vial was charged with tert-butyl N-[(3S,7S,8S,9S)-8-(4-bromophenoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate (34 mg, 0.057 mmol), phenylboronic acid (19 mg, 0.156 mmol), Na₂CO₃ (18.0 mg, 0.170 mmol) and Pd(PPh₃)₄ (6.54 mg, 5.66 μmol). The vial was evacuated and backfilled with N₂ (repeated 3×), dioxane (425 μl) and water (142 μl) were added, and the vial was fitted with an air condenser and the reaction mixture was heated at 80° C. for 3 h. The cooled reaction mixture was diluted with CH₂Cl₂, passed through a phase separator cartridge, concentrated, and the residue purified by silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (25 mg, 74%) as a white solid: ¹H NMR (400 MHz, CDCl₃) δ 7.59-7.53 (m, 2H), 7.51-7.46 (m, 2H), 7.47-7.37 (m, 2H), 7.36-7.26 (m, 1H), 7.18-7.09 (m, 2H), 4.94-4.79 (m, 2H), 4.40 (dd, J=9.6, 7.3 Hz, 1H), 3.56 (ddd, J=7.1, 5.1, 1.9 Hz, 1H), 3.47 (dt, J=9.0, 6.6 Hz, 1H), 3.26 (dt, J=9.1, 6.5 Hz, 1H), 2.49-2.35 (m, 1H), 2.25-2.12 (m, 1H), 2.13-2.01 (m, 1H), 1.86-1.66 (m, 2H), 1.52 (s, 18H), 1.48-1.39 (m, 2H), 1.37 (d, J=6.3 Hz, 3H), 1.08 (ddt, J=15.9, 7.5, 1.9 Hz, 1H), 0.77 (t, J=7.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 170.86, 159.35, 152.89, 140.82, 134.28, 128.69, 127.99, 126.74, 126.66, 116.75, 83.07, 83.04, 82.75, 72.67, 71.42, 57.42, 30.59, 28.76, 27.99, 23.19, 19.30, 18.26, 10.57; ESIMS m/z 620 ([M+Na]⁺).

Example 23 Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-methoxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate

To a solution of a tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (1.00 g, 2.19 mmol) in CH₂Cl₂ (21.86 ml) at 0° C. was added Proton Sponge® (0.937 g, 4.37 mmol) followed by trimethyloxonium tetrafluoroborate (0.485 g, 3.28 mmol). The mixture was stirred at 0° C. for 30 min, warmed to ambient temperature, stirred for an additional 30 min, and then poured into sat. aqueous NaHCO₃ (50 mL) and extracted with CH₂Cl₂ (3×50 mL). The combined organic extracts were washed with 10% NaHSO₄ (2×50 mL), washed with brine (50 mL), and dried by passing through a phase-separation cartridge. The filtrate was concentrated and the crude foam was purified via flash chromatography (SiO₂, 0→35% EtOAc/hexane) to afford the title product as a clear oil (1.03 g, 100%): ¹H NMR (400 MHz, CDCl₃) δ 4.98 (dd, J=2.0, 0.9 Hz, 1H), 4.91-4.85 (m, 1H), 4.82 (dd, J=10.4, 8.1 Hz, 1H), 4.62 (dq, J=9.7, 6.3 Hz, 1H), 3.98 (d, J=12.1 Hz, 1H), 3.86 (d, J=12.1 Hz, 1H), 3.56 (s, 3H), 3.40 (ddd, J=7.0, 5.1, 1.7 Hz, 1H), 3.27 (dd, J=9.6, 7.3 Hz, 1H), 2.43-2.29 (m, 1H), 2.17-1.97 (m, 2H), 1.77 (s, 3H), 1.74-1.58 (m, 2H), 1.51 (s, 18H), 1.39 (d, J=6.3 Hz, 3H), 1.01-0.88 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 170.84, 152.88, 142.53, 112.15, 85.57, 83.24, 82.65, 73.03, 72.89, 61.32, 57.36, 30.55, 28.40, 27.96, 19.57, 19.17, 17.87; HRMS-ESI (m/z) [M+Na]⁺ calcd for C₂₄H₄₁NNaO₈, 494.2734; found, 494.2724.

Example A Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Mycosphaerella graminicola; Anamorph: Septoria tritici; Bayer Code SEPTTR)

Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 110 ppm Triton X-100. The fungicide solutions were applied onto wheat seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling. All fungicides were evaluated using the aforementioned method for their activity vs. all target diseases. Wheat leaf blotch and brown rust activity were also evaluated using track spray applications, in which case the fungicides were formulated as EC formulations, containing 0.1% Trycol 5941 in the spray solutions.

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Septoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. When disease symptoms were fully expressed on the 1^(st) leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.

Example B Evaluation of Fungicidal Activity: Wheat Brown Rust (Puccinia triticina; Synonym: Puccinia recondite f. sp. tritici; Bayer Code PUCCRT)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22° C. with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example C Evaluation of Fungicidal Activity: Wheat Glume Blotch (Leptosphaeria nodorum; Bayer Code LEPTNO)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example D Evaluation of Fungicidal Activity: Apple Scab (Venturia inaequalis; Bayer Code VENTIN)

Apple seedlings (variety McIntosh) were grown in soil-less Metro mix, with one plant per pot. Seedlings with two expanding young leaves at the top (older leaves at bottom of the plants were trimmed) were used in the test. Plants were inoculated with a spore suspension of Venturia inaequalis 24 hr after fungicide treatment and kept in a 22° C. dew chamber with 100% RH for 48 hr, and then moved to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example E Evaluation of Fungicidal Activity: Grape Powdery Mildew (Uncinula necator; Bayer Code UNCINE)

Grape seedlings (variety Carignane) were grown in soil-less Metro mix, with one plant per pot, and used in the test when approximately one month old. Plants were inoculated 24 hr after fungicide treatment by shaking spores from infected leaves over test plants. Plants were maintained in a greenhouse set at 20° C. until disease was fully developed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example F Evaluation of Fungicidal Activity: Powdery Mildew of Cucumber (Erysiphe cichoracearum; Bayer Code ERYSCI)

Cucumber seedlings (variety Bush Pickle) were grown in soil-less Metro mix, with one plant per pot, and used in the test when 12 to 14 days old. Plants were inoculated with a spore suspension 24 hr following fungicide treatments. After inoculation the plants remained in the greenhouse set at 20° C. until disease was fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example G Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer Code CERCBE)

Sugar beet plants (variety HH88) were grown in soil-less Metro mix and trimmed regularly to maintain a uniform plant size prior to test. Plants were inoculated with a spore suspension 24 hr after fungicide treatments. Inoculated plants were kept in a dew chamber at 22° C. for 48 hr then incubated in a greenhouse set at 24° C. under a clear plastic hood with bottom ventilation until disease symptoms were fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example H Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi; Bayer Code PHAKPA)

Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 0.011% Tween 20. The fungicide solutions were applied onto soybean seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling.

Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22° C. and 100% RH then transferred to a growth room at 23° C. for disease to develop. Disease severity was assessed on the sprayed leaves.

Example I Evaluation of Fungicidal Activity: Wheat Powdery Mildew (Blumeria graminis f. sp. tritici; Synonym: Erysiphe graminis f. sp. tritici; Bayer Code ERYSGT)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated by dusting with infected stock plants 24 hr after fungicide treatments. After inoculation the plants were kept in a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example J Evaluation of Fungicidal Activity: Barley Powdery Mildew (Blumeria graminis f. sp. hordei; Synonym: Erysiphe graminis f. sp. hordei; Bayer Code ERYSGH)

Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by dusting with infected stock plants 24 hr after fungicide treatments. After inoculation the plants were kept in a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example K Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis; Bayer Code RHYNSE)

Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 20° C. with 100% relative humidity for 48 hr. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example L Evaluation of Fungicidal Activity: Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae; Bayer Code PYRIOR)

Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example M Evaluation of Fungicidal Activity: Tomato Early Blight (Alternaria solani; Bayer Code ALTESO)

Tomato plants (variety Outdoor girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example N Evaluation of Fungicidal Activity: Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotrichum lagenarium; Bayer Code COLLLA)

Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

TABLE 1 Structure and Preparation Method for F Series Compounds Prepared According Compound to Number Structure Example F1

11 F2

12, 12A F3

12, 12B (1-3) F4

12, 12B (1-3) F5

12, 12C (1-2) F6

12, 12A F7

13, 13B (1-3) F8

13, 13B (1) And 13D (1, 2) F9

13, 13B (1) and 13D (1-2) F10

13, 13E (1-3) F11

13, 13F (1-3) F12

14, 14A F13

15 (1-4) F14

16A F15

17A F16

17B F17

17C F18

17D F19

16A F20

17A F21

16B F22

16B F23

16B F24

16B F25

16B F26

17A F27

16A F28

17A F29

17A F30

17A F31

17A F32

17A F33

16A F34

17B F35

17B F36

17B F37

17B F38

17B F39

17A F40

16A F41

16A F42

17C F43

17A F44

17A F45

17A F46

17A F47

17C F48

17A F49

17B F50

16A F51

17B F52

17B F53

16A F54

16A F55

16A F56

16A F57

16A F58

17C F59

17A F60

17A F61

17A F62

17B F63

17A F64

16A F65

16A F66

17A F67

17B F68

17A F69

17B F70

16A F71

16A F72

17A F73

16A F74

16A F75

16A F76

17B F77

17C F78

17A F79

17B F80

17A F81

17C F82

16A F83

17C F84

16A F85

16A F86

17A F87

17A F88

17A F89

17C F90

17C F91

17C F92

17C F93

16A F94

16A F95

17A F96

17A F97

17B F98

17B F99

17B F100

17B F101

17B F102

17C F103

17C F104

16A F105

16A F106

17A F107

17A F108

17B F109

17C F110

17D F111

16A F112

17B F113

16A F114

16A F115

17A F116

17A F117

16A F118

16A F119

16A F120

16A F121

17A F122

17A F123

17B F124

17B F125

17A F126

17B F127

16A F128

16A F129

16A F130

17A F131

17C F132

17D F133

17A F134

17C F135

17A F136

17B F137

17C F138

17A F139

17B F140

17D F141

17C F142

16A F143

16A F144

17A F145

17B F146

17D F147

17D F148

17A F149

16A F150

17A F151

17C F152

17D F153

16A F154

17B F155

17A F156

16A F157

17B F158

17A F159

17C F160

16A F161

17B F162

17A F163

16A F164

16A F165

17A F166

17A F167

16A F168

16A F169

17B F170

17A F171

17B F172

17A F173

17C F174

13, 13F (1-3) F175

13, 13F (1-3) F176

13, 13F (1-3) F177

12, 12C (1-2) F178

12, 12B (1-3) F179

12, 12B (1-3) F180

13, 13B (1) F181

13, 13B (1) and 13F (1, 3) F182

12, 12C (1-2) F183

12, 12B (1-3) F184

13, 13F (1-3) or 13A (1-2) F185

13, 13C (1-3) F186

13, 13B (1-3) F187

13, 13A (1-2) F188

12, 12B (1-3) F189

12, 12B (1-3) F190

13, 13A (2) F191

12, 12B (1, 3) F192

12, 12B (1-3) F193

12, 12B (1-3) F194

12, 12A F195

12, 12B (1-3) F196

12, 12B (1-3) F197

12, 12B (1-3) F198

13, 13F (1-3) F199

13, 13F (1-3) F200

13, 13G (1-3) F201

13, 13B (1) and 13D (1-2) F202

13, 13B (1) and 13D (1-2) F203

13, 13A (1-2) F204

13, 13G (1-3) F205

13, 13B (1) and 13D (1-2) F206

12, 12B (1-3) F207

13, 13F (1-3) F208

13, 13F (1-3) F209

13, 13G (1-3) F210

16A F211

16A F212

16A F213

16A F214

17C F215

17D F216

17C F217

17A F218

17B F219

16A F220

16A F221

16A F222

17A F223

17A F224

16A F225

17A F226

13, 13B (1) and 13F (1, 3) F227

13, 13G (1-3) F228

13, 13G (1-3) F229

12, 12B (1-3) F230

13, 13G (1-3) F231

12, 13D (1-2) F232

16A F233

17A F234

17B F235

17C F236

17C F237

17B F238

12, 13D (1-2) F239

16A F240

17A F241

17B F242

17C F243

17D F244

13, 23, 12A F245

16A F246

13, 23, 13B (1, 3) F247

16A F248

12, 23, 12A F249

16A F250

17A F251

17A F252

17A F253

17B F254

17B F255

17B F256

17C F257

17C F258

17C F259

17D F260

17D F261

12, 12B (1-3) F262

16A F263

12, 12B (1-3) F264

16A F265

17A F266

17C F267

17A F268

12, 12B (1-3) F269

20, 12B (1-3) F270

16A F271

16A F272

16A F273

16A F274

17C F275

17C F276

12, 12B (1-3) F277

12, 12B (1-2), 21, 12A F278

20, 12B (1-3) F279

12, 12B (1-3) F280

16A F281

16A F282

17C F283

16A F284

17C F285

17C F286

17C F287

17C F288

16A F289

17C F290

16A F291

17C F292

12, 12B (1-2), 21, 22 12A F293

12, 12B (1-3) F294

12, 12B (1-2), 21, 22 12A

TABLE 2 Analytical Data for F Series Compounds *Mass. *¹³C NMR; *Cmpd. No. *Phys. Apps. *MP *IR Spec. *¹H NMR *¹⁹F NMR F1 White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Crystalline (m/z) 4.84 (dd, J = 10.0, (CDCl₃) δ Solid [M + Na]⁺ 7.4 Hz, 1H), 4.72 (dq, 170.82, calcd for J = 9.1, 6.3 Hz, 1H), 152.88, 82.85, C₁₉H₃₃NNaO₈, 3.59-3.41 (m, 2H), 73.79, 73.28, 426.2102; 2.70-2.58 (m, 1H), 57.70, 35.10, found, 2.42-2.27 (m, 1H), 30.87, 29.22, 426.2098 2.12-2.00 (m, 1H), 27.95, 19.98, 1.96-1.63 (m, 3H), 18.06 1.59-1.46 (m, 18H), 1.42 (d, J = 6.3 Hz, 3H) F2 White Foam — — ESI-MS ¹H NMR (CDCl₃) δ ¹³C NMR m/z 356.5 8.74 (s, 3H), (CDCl₃) δ ([M + H]⁺) 7.20 (dd, J = 15.3, 7.6 Hz, 170.00, 4H), 7.01 (d, J = 8.0 Hz, 159.33, 2H), 6.92 (dt, J = 14.2, 157.42, 7.3 Hz, 2H), 129.47, 6.81 (d, J = 8.0 Hz, 129.46, 2H), 1.90-1.64 (m, 121.76, 3H), 5.08 (t, J = 7.0 Hz, 121.59, 1H), 4.60 (t, J = 8.1 Hz, 116.69, 1H), 4.50 (br 116.48, 82.15, s, 1H), 4.16 (br s, 81.87, 73.49, 1H), 2.57 (br s, 1H), 52.29, 30.92, 2.30 (br s, 1H), 28.28, 18.11, 1.38 (d, J = 5.7 Hz, 3H), 17.88 1.13 (d, J = 10.0 Hz, 1H) F3 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.73 (br s, 3H), (CDCl₃) δ [M + H]⁺ 7.28-7.21 (m, 2H), 170.08, calcd for 7.04 (d, J = 7.9 Hz, 2H), 159.50, C₁₉H₃₀NO₄, 6.94 (t, J = 7.3 Hz, 129.35, 336.2169; 1H), 4.98 (dq, J = 12.7, 121.39, found, 6.1 Hz, 1H), 116.34, 82.82, 336.2173 4.37 (dd, J = 9.3, 7.4 Hz, 82.50, 76.39, 1H), 4.11 (t, J = 8.3 Hz, 73.64, 52.28, 1H), 3.70 (s, 31.07, 28.67, 1H), 3.22 (dd, J = 8.7, 27.87, 19.33, 6.6 Hz, 1H), 19.18, 18.00, 3.03 (dd, J = 8.7, 6.2 Hz, 17.87 1H), 2.58 (s, 1H), 2.28-2.15 (m, 1H), 1.90-1.59 (m, 4H), 1.34 (d, J = 6.3 Hz, 3H), 0.98 (d, J = 9.3 Hz, 1H), 0.77 (d, J = 6.7 Hz, 3H), 0.72 (d, J = 6.7 Hz, 3H) F4 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.65 (br s, 3H), (CDCl₃) δ [M + H]⁺ 7.25 (t, J = 7.9 Hz, 2H), 170.02, calcd for 7.00-6.84 (m, 3H), 157.44, C₁₉H₃₀NO₄, 4.93-4.68 (m, 1H), 129.50, 336.2169; 4.34 (br s, 1H), 121.27, found, 4.09 (br s, 1H), 116.49, 83.14, 336.2167 3.61-3.46 (m, 2H), 82.78, 80.70, 3.36 (dd, J = 8.5, 6.7 Hz, 73.85, 52.21, 1H), 2.49 (br s, 1H), 30.85, 28.97, 1.89-1.51 (m, 4H), 28.16, 19.37, 1.43 (d, J = 6.0 Hz, 19.27, 17.91, 3H), 1.05-0.87 (m, 17.76 1H), 0.82 (d, J = 6.7 Hz, 3H), 0.78 (d, J = 6.7 Hz, 3H) F5 Colorless — — ESIMS ¹H NMR (CDCl₃) ¹³C NMR Solid m/z 404.2 δ 8.65 (bs, 3H), (CDCl₃) δ ([M + H]⁺) 7.02-6.86 (m, 4H), 170.11, 6.82-6.67 (m, 4H), 157.86 (d, J = 239.9 Hz), 5.07-4.96 (m, 1H), 155.67 (d, J = 2.0 Hz), 4.44 (dd, J = 9.4, 7.3 Hz, 154.77, 1H), 4.34-4.26 (m, 151.39, 1H), 4.21-4.08 (m, 118.40, 1H), 3.70 (s, 3H), 117.88 (d, J = 8.1 Hz), 3.38-3.04 (m, 1H), 115.97 (d, J = 23.0 Hz), 2.63-2.51 (m, 1H), 114.74, 83.58, 2.30-2.13 (m, 1H), 83.43, 73.46, 1.85-1.69 (m, 2H), 55.72, 52.40, 1.37 (d, J = 6.3 Hz, 31.01, 28.32, 3H), 1.10-0.98 (m, 18.19, 18.02; 1H) ¹⁹F NMR (CDCl₃) δ −122.33 F6 Chalky 188-230 — ESIMS ¹H NMR (CDCl₃) δ — White Solid m/z 316.6 8.69 (s, 2H), 4.75 (s, ([M + H]⁺) 1H), 4.00 (s, 1H), 3.60 (dd, J = 8.6, 6.2 Hz, 1H), 3.36-3.28 (m, 3H), 3.28-3.20 (m, 1H), 3.09 (dd, J = 8.6, 6.3 Hz, 1H), 2.51 (s, 1H), 2.13 (s, 1H), 1.88-1.52 (m, 6H), 1.39 (d, J = 6.2 Hz, 3H), 0.96-0.85 (m, 12H) F7 White Solid 199-202 3395, HRMS-ESI ¹H NMR (CD₃OD) δ ¹³C NMR 2947, (m/z) 7.07-6.94 (m, 2H), (CD₃OD) δ 2093, [M + H]⁺ 6.90-6.71 (m, 2H), 169.76, 1745, calcd for 5.01 (dq, J = 9.4, 6.4 Hz, 154.43, 1506 C₂₀H₃₂NO₅, 1H), 4.32 (dd, J = 9.5, 153.69, 366.2275; 7.3 Hz, 1H), 117.00, found, 3.98 (dd, J = 10.8, 7.5 Hz, 114.06, 82.99, 366.2275 1H), 3.74 (s, 3H), 82.91, 76.03, 3.64-3.48 (m, 1H), 73.61, 54.67, 3.30-3.27 (m, 1H), 51.40, 30.61, 3.08 (dd, J = 8.8, 6.1 Hz, 28.58, 27.32, 1H), 18.35, 18.23, 2.40-2.18 (m, 2H), 17.41, 17.02 1.89-1.71 (m, 2H), 1.65 (dq, J = 13.2, 6.6 Hz, 1H), 1.56-1.42 (m, 1H), 1.36 (d, J = 6.4 Hz, 3H), 0.95 (dd, J = 11.5, 7.3 Hz, 1H), 0.78 (dd, J = 16.4, 6.7 Hz, 6H) F8 White Solid — — ESIMS — — m/z 356.3 ([M + H]⁺) F9 White Solid — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR m/z 356 5.11 (dd, J = 9.7, 7.9 Hz, (CD₃OD) δ ([M + H]⁺) 1H), 4.99 (dq, J = 9.7, 177.44, 6.3 Hz, 1H), 171.22, 82.37, 3.99 (dd, J = 10.8, 7.5 Hz, 77.16, 76.44, 1H), 3.46 (ddd, J = 7.4, 73.86, 52.81, 5.1, 1.8 Hz, 1H), 45.17, 31.99, 3.37-3.32 (m, 1H), 31.11, 30.86, 3.02 (dd, J = 8.7, 6.5 Hz, 30.01, 28.36, 1H), 26.78, 26.69, 2.87-2.73 (m, 1H), 19.77, 19.72, 2.37-2.20 (m, 2H), 18.51, 17.57 1.99-1.55 (m, 12H), 1.55-1.41 (m, 1H), 1.27 (d, J = 6.3 Hz, 3H), 0.92 (dtd, J = 15.1, 4.8, 2.4 Hz, 1H), 0.86 (dd, J = 6.7, 1.2 Hz, 6H) F10 White Solid 231-235 2944, HRMS-ESI ¹H NMR (CD₃OD) δ ¹³C NMR 2870, (m/z) 5.13 (dd, J = 9.8, 7.8 Hz, (CD₃OD) δ 2106, [M + Na]⁺ 1H), 174.56, 1742, calcd for 5.08-4.96 (m, 1H), 4.01 (dd, J = 10.7, 169.88, 81.00, 1727, C₁₇H₂₉NNaO₅, 7.5 Hz, 1H), 75.96, 75.24, 1225 350.1938; 3.49 (ddd, J = 7.6, 72.42, 51.38, found, 5.2, 1.8 Hz, 1H), 30.64, 28.52, 350.1937 3.38 (dd, J = 8.8, 6.0 Hz, 27.12, 18.29, 1H), 3.05 (dd, J = 8.8, 18.21, 17.08, 6.7 Hz, 1H), 16.01, 12.23, 2.44-2.20 (m, 2H), 7.69, 7.57 1.86-1.61 (m, 4H), 1.59-1.42 (m, 1H), 1.30 (d, J = 6.3 Hz, 3H), 1.02-0.90 (m, 5H), 0.90 (dd, J = 6.6, 2.3 Hz, 6H) F11 White Solid 236-240 2943, — ¹H NMR (CD₃OD) δ ¹³C NMR 2900, 4.87-4.75 (m, 1H), (CD₃OD) δ 2872, 3.97-3.80 (m, 2H), 169.81, 83.65, 2109, 3.71 (dt, J = 9.3, 6.2 Hz, 83.58, 75.37, 1743, 1H), 73.68, 71.34, 1453, 3.43-3.35 (m, 3H), 3.14 (dd, J = 8.7, 51.39, 30.56, 1253 6.0 Hz, 1H), 30.21 (q, J = 28.7 Hz), 2.33-2.12 (m, 4H), 28.74, 26.95, 1.89-1.72 (m, 3H), 22.90-22.61 (m), 18.51, 1.68 (dq, J = 9.5, 4.6 Hz, 18.39, 17.35, 2H), 1.52-1.35 (m, 16.81; 4H), 0.93 (dd, J = 6.7, ¹⁹F NMR 3.7 Hz, 6H), (CD₃OD) δ 0.85 (dt, J = 16.3, 4.8 Hz, −69.61 (t, J = 11.3 Hz) 1H) F12 Flaky — 3455, HRMS-ESI ¹H NMR (CD₃OD) δ ¹³C NMR Brown Solid 2951, (m/z) 5.21 (dd, J = 9.7, 8.0 Hz, (CD₃OD) δ 2870, [M + H]⁺ 1H), 5.14 (dq, J = 9.7, 175.65, 1732, calcd for 6.2 Hz, 1H), 169.83, 74.39, 1184, C₂₁H₃₄NO₆, 5.03 (ddd, J = 7.7, 5.4, 2.2 Hz, 73.59, 72.07, 1144 396.2381; 1H), 4.03 (t, J = 9.1 Hz, 51.35, 43.64, found, 1H), 43.52, 30.54, 396.2372 2.73 (dtt, J = 24.0, 8.7, 6.9 Hz, 29.57, 29.53, 2H), 2.30 (dt, J = 13.9, 29.44, 28.72, 7.1 Hz, 1H), 25.31, 25.25, 2.21-2.08 (m, 1H), 17.29, 16.10 1.95-1.54 (m, 18H), 1.48 (q, J = 12.6, 12.1 Hz, 1H), 1.30 (d, J = 6.2 Hz, 3H), 1.15 (ddt, J = 16.3, 7.6, 2.4 Hz, 1H) F13 Greasy — 2955, HRMS-ESI — ¹³C NMR White Solid 2873, (m/z) (CD₃OD) δ 1748, [M + H]⁺ 169.78, 1223, calcd for 169.75, 85.14, 1103 C₁₈H₃₆NO₅, 83.88, 83.69, 346.2588; 83.42, 75.56, found, 75.48, 75.46, 346.2596 73.85, 73.66, 73.09, 60.22, 51.39, 32.19, 30.53, 28.75, 28.72, 27.28, 27.26, 27.17, 19.04, 18.44, 18.41, 17.39, 16.77, 16.63, 12.88 F14 White Foam — 3373, ESIMS ¹H NMR (CDCl₃) δ ¹³CNMR 2923, m/z 463.3 12.08 (s, 1H), (CDCl₃) δ 2853, ([M + H]⁺); 8.47 (d, J = 8.1 Hz, 1H), 172.12, 1740, HRMS-ESI 7.99 (d, J = 5.1 Hz, 168.78, 1650, (m/z) 1H), 6.87 (d, J = 5.2 Hz, 155.47, 1575, [M + H]⁺ 1H), 4.97 (dq, J = 2.8, 148.84, 1527, calcd for 1.4 Hz, 2H), 142.56, 1448, C₂₄H₃₄N₂O₇, 4.87 (dq, J = 4.7, 2.2 Hz, 142.50, 1441 463.2433; 2H), 4.90-4.82 (m, 140.65, found, 1H), 4.60 (dt, J = 10.8, 130.50, 463.2439 7.6 Hz, 1H), 112.25, 4.28 (d, J = 11.7 Hz, 112.12, 1H), 4.05 (d, J = 11.7 Hz, 109.60, 83.77, 1H), 3.97 (d, J = 12.4 Hz, 83.62, 73.30, 1H), 3.94 (s, 73.24, 56.20, 3H), 3.85 (d, J = 11.6 Hz, 51.43, 33.42, 1H), 29.54, 28.08, 3.57-3.42 (m, 2H), 2.38 (dtd, J = 13.7, 19.93, 19.81, 7.1, 6.7, 1.8 Hz, 18.40, 18.12 1H), 2.09-2.20 (m, 1H), 1.79-1.74 (m, 6H), 1.75-1.66 (m, 1H), 1.61-1.54 (m, 2H), 1.49-1.37 (m, 3H), 0.90-0.80 (m, 1H); F15 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Oil 2924, (m/z) 8.32 (d, J = 8.1 Hz, (CDCl₃) δ 2854, [M + H]⁺ 1H), 8.28 (dd, J = 5.3, 172.59, 1745, calcd for 1.8 Hz, 1H), 6.95 (d, 170.26, 1676, C₂₇H₃₉N₂O₉, J = 5.3 Hz, 1H), 162.96, 1502 535.2650; 5.74 (d, J = 1.7 Hz, 2H), 160.25, found, 4.97 (s, 2H), 4.87 (d, 145.72, 535.2644 J = 2.6 Hz, 2H), 143.95, 4.85-4.79 (m, 1H), 142.46, 4.61 (dt, J = 10.1, 7.6 Hz, 142.40, 1H), 4.28 (d, J = 11.7 Hz, 142.38, 1H), 4.05 (d, J = 11.7 Hz, 112.08, 1H), 3.95 (d, 111.94, J = 12.1 Hz, 1H), 109.61, 89.50, 3.91 (s, 3H), 3.85 (d, 83.69, 83.56, J = 11.6 Hz, 1H), 73.07, 72.88, 3.51-3.45 (m, 2H), 56.18, 51.62, 2.38 (dt, J = 13.6, 6.8 Hz, 33.35, 29.41, 1H), 28.01, 20.86, 2.21-2.08 (m, 1H), 2.07 (s, 3H), 19.79, 19.68, 1.75 (s, 6H), 18.33, 17.97 1.74-1.61 (m, 1H), 1.56 (d, J = 3.6 Hz, 1H), 1.42 (d, J = 6.5 Hz, 3H), 1.40-1.29 (m, 1H), 1.03-0.79 (m, 1H) F16 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Oil 2974, (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ 2934, [M + H]⁺ 1H), 8.27 (d, J = 5.1 Hz, 176.24, 1744, calcd for 1H), 6.94 (d, J = 5.3 Hz, 172.60, 1677, C₂₇H₃₉N₂O₉, 1H), 162.94, 1503, 563.2963; 5.79-5.74 (m, 2H), 4.97 (s, 160.23, 1455 found, 2H), 4.89-4.81 (m, 145.59, 563.2974 1H), 4.87-4.79 (s, 144.19, 2H), 4.61 (q, J = 8.0 Hz, 142.47, 1H), 4.27 (d, J = 11.6 Hz, 142.42, 1H), 142.06, 4.04 (d, J = 11.7 Hz, 1H), 112.08, 3.96 (d, J = 12.0 Hz, 111.95, 1H), 3.89 (s, 3H), 109.54, 89.89, 3.85 (d, J = 11.7 Hz, 83.71, 83.58, 1H), 3.55-3.41 (m, 73.08, 72.88, 2H), 2.55 (p, J = 7.0 Hz, 56.13, 51.62, 1H), 2.38 (dt, J = 13.5, 33.85, 33.38, 6.7 Hz, 1H), 29.69, 29.41, 2.21-2.06 (m, 1H), 28.02, 19.80, 1.75 (s, 6H), 19.69, 18.67, 1.73-1.59 (m, 1H), 18.34, 17.98 1.56 (m, 1H), 1.41 (d, J = 6.3 Hz, 3H), 1.41-1.27 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.96 (dd, J = 15.0, 7.1 Hz, 1H) F17 Colorless — 3378, HRMS-ESI ¹HNMR (CDCl₃) δ ¹³CNMR Oil 2954 (m/z) 8.59-8.46 (m, 1H), (CDCl₃) δ 2873, [M + H]⁺ 8.33 (d, J = 5.4 Hz, 172.52, 1772, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.91, 1744, C₂₆H₃₉N₂O₈, 1H), 4.97 (s, 1H), 162.38, 1679, 507.2705; 4.87 (s, 1H), 159.43, 1508 found, 4.80 (dq, J = 9.2, 6.4 Hz, 146.69, 507.2701 1H), 4.59 (ddd, J = 10.8, 142.52, 8.4, 7.2 Hz, 141.42, 1H), 3.95 (d, J = 12.0 Hz, 137.48, 1H), 3.90 (s, 3H), 112.13, 3.84 (d, J = 12.0 Hz, 109.78, 83.82, 1H), 3.63 (dd, J = 8.6, 83.68, 80.67, 6.1 Hz, 1H), 73.25, 73.12, 3.47-3.32 (m, 3H), 56.29, 51.35, 2.40 (s, 3H), 33.63, 29.12, 2.39-2.30 (m, 1H), 2.11 (dddd, 28.05, 20.76, J = 15.7, 10.2, 8.1, 19.72, 19.54, 5.1 Hz, 1H), 1.83 (dt, 19.38, 18.30, J = 13.3, 6.6 Hz, 1H), 17.93 1.76 (t, J = 1.1 Hz, 3H), 1.73-1.59 (m, 2H), 1.39 (d, J = 6.3 Hz, 3H), 1.36-1.26 (m, 1H), 0.95 (dt, J = 7.4, 2.1 Hz, 1H), 0.91 (d, J = 6.7 Hz, 3H), 0.89 (d, J = 6.8 Hz, 3H) F18 White Solid 73-77 2935, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 1744, (m/z) 8.53-8.46 (m, 1H), (CDCl₃) δ 1679, [M + H]⁺ 8.32 (d, J = 5.4 Hz, 172.56, 1508 calcd for 1H), 6.99 (d, J = 5.5 Hz, 169.39, C₂₈H₄₃N₂O₉, 1H), 4.77 (dq, J = 9.6, 162.31, 551.2963; 6.4 Hz, 1H), 159.41, found, 4.58 (ddd, J = 10.7, 8.4, 146.73, 551.2968 7.3 Hz, 1H), 141.44, 4.01 (ddd, J = 8.0, 5.5, 3.4 Hz, 137.31, 1H), 3.89 (s, 3H), 109.77, 83.74, 3.81 (t, J = 6.6 Hz, 81.75, 79.15, 2H), 3.77 (dt, J = 8.8, 75.80, 73.15, 6.6 Hz, 1H), 3.54 (dt, 67.56, 58.77, J = 8.7, 6.8 Hz, 1H), 56.30, 51.31, 3.44-3.38 (m, 1H), 34.61, 33.68, 3.40 (s, 3H), 33.51, 31.88, 3.30 (dd, J = 9.6, 7.3 Hz, 28.42, 23.64, 1H), 2.98 (t, J = 6.6 Hz, 23.52, 23.33, 2H), 18.49, 17.81, 2.40-2.28 (m, 1H), 10.65 2.14-1.99 (m, 1H), 1.78-1.46 (m, 12H), 1.38 (d, J = 6.3 Hz, 3H), 1.35-1.26 (m, 1H), 0.92 (t, J = 7.4 Hz, 3H), 0.90-0.83 (m, 1H) F19 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Foam (m/z) 12.04 (s, 1H), (CDCl₃) δ [M + H]⁺ 8.48 (d, J = 8.1 Hz, 1H), 171.93, calcd for 7.99 (d, J = 5.2 Hz, 168.73, C₂₈H₃₀N₂O₇, 1H), 7.30-7.13 (m, 159.50, 506.2053; 4H), 7.11-7.01 (m, 157.55, found, 2H), 7.01-6.88 (m, 155.38, 506.2053 2H), 6.88-6.79 (m, 148.76, 3H), 5.15 (dq, J = 9.5, 140.57, 6.4 Hz, 1H), 130.32, 4.76-4.60 (m, 2H), 129.46, 4.60-4.45 (m, 1H), 129.45, 3.93 (s, 3H), 2.41 (dt, J = 13.7, 121.68, 7.0 Hz, 1H), 121.59, 2.36-2.18 (m, 1H), 116.90, 1.99-1.84 (m, 1H), 116.54, 1.77 (dt, J = 16.0, 7.8 Hz, 109.54, 82.38, 1H), 82.30, 72.71, 1.46-1.34 (m, 4H), 1.18 (dd, J = 16.1, 56.09, 51.26, 7.8 Hz, 1H) 33.22, 28.18, 18.29, 18.20 F20 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) ¹³C NMR (m/z) δ 8.33 (d, J = 8.0 Hz, (CDCl₃) [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, δ 172.54, calcd for 1H), 170.30, C₃₁H₃₅N₂O₉, 7.26-7.16 (m, 5H), 163.02, 579.2337; 7.10-7.02 (m, 2H), 160.29, found, 6.99-6.88 (m, 3H), 159.53, 578.2234 6.88-6.81 (m, 2H), 5.74 (s, 2H), 157.59, 5.13 (dq, J = 9.5, 6.4 Hz, 145.74, 1H), 144.06, 4.75-4.62 (m, 2H), 142.29, 4.57-4.49 (m, 1H), 3.91 (s, 3H), 129.42, 2.42 (dt, J = 13.6, 7.1 Hz, 121.62, 1H), 121.52, 2.36-2.21 (m, 1H), 2.07 (s, 3H), 116.91, 1.98-1.87 (m, 1H), 116.54, 1.74 (dq, J = 15.5, 109.66, 89.53, 7.8 Hz, 1H), 1.63 (s, 82.44, 82.38, 1H), 1.42 (d, J = 6.4 Hz, 72.44, 56.20, 3H), 51.61, 33.29, 1.40-1.28 (m, 1H), 1.19 (dd, J = 16.1, 28.27, 20.89, 7.7 Hz, 1H) 18.37, 18.19 F21 Hard White 94-95 — HRMS-ESI ¹H NMR (CDCl₃) ¹³C NMR Foam (m/z) δ 12.09 (d, J = 0.4 Hz, (CDCl₃) [M + Na]⁺ 1H), 8.47 (d, J = 8.2 Hz, δ 172.05, calcd for 1H), 7.99 (d, 168.65, C₂₄H₃₈N₂O₇Na, J = 5.2 Hz, 1H), 155.34, 489.2571; 6.86 (d, J = 5.2 Hz, 1H), 148.72, found, 4.81 (pd, J = 6.3, 2.0 Hz, 140.51, 489.2567 1H), 4.58 (dt, J = 10.8, 130.42, 7.6 Hz, 1H), 109.46, 84.19, 3.94 (s, 3H), 83.70, 80.50, 3.62 (dd, J = 8.6, 6.2 Hz, 75.84, 73.34, 1H), 3.42-3.31 (m, 56.07, 51.31, 3H), 3.28 (dd, J = 8.7, 33.34, 29.09, 6.5 Hz, 1H), 28.90, 27.63, 3.12 (dd, J = 8.7, 6.3 Hz, 19.57, 19.54, 1H), 2.37 (dt, J = 13.8, 19.39, 18.24, 6.5 Hz, 1H), 18.00 2.24-2.06 (m, 1H), 1.82 (dpd, J = 13.2, 6.6, 3.5 Hz, 2H), 1.75-1.58 (m, 2H), 1.45-1.30 (m, 4H), 0.96-0.86 (m, 13H) F22 Hard White 47-52 3348, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Foam 3029, (m/z) 12.09 (d, J = 3.1 Hz, (CDCl₃) 2941, [M + H]⁺ 1H), 8.49 (d, J = 8.0 Hz, δ 172.03, 2875, calcd for 1H), 7.97 (d, J = 5.2 Hz, 168.72, 1743, C₃₀H₃₅N₂O₇, 1H), 155.35, 1649, 535.2439; 7.42-7.19 (m, 10H), 148.74, 1576, found, 6.84 (dd, J = 5.1, 1.5 Hz, 140.57, 1528, 535.2433 1H), 4.96-4.80 (m, 138.41, 1497, 2H), 4.69 (d, J = 10.9 Hz, 138.33, 1481, 1H), 130.37, 1450, 4.66-4.53 (m, 2H), 128.43, 1327, 4.53-4.44 (m, 1H), 3.91 (d, J = 2.3 Hz, 128.40, 1242, 3H), 3.66 (d, 127.96, 1216, J = 7.6 Hz, 2H), 127.83, 1059, 2.38 (dt, J = 13.6, 6.7 Hz, 127.75, 800 1H), 2.30-2.11 (m, 127.69, 1H), 1.88-1.61 (m, 109.54, 83.89, 2H), 1.49-1.32 (m, 83.64, 75.75, 4H), 1.01 (dd, J = 16.1, 73.13, 71.22, 7.3 Hz, 1H) 56.09, 51.33, 33.27, 27.96, 18.35, 18.13 F23 Hard White 58-64 3364, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Foam 2940, (m/z) 12.06 (s, 1H), (CDCl₃) 1744, [M + H]⁺ 8.58-8.37 (m, 1H), 7.98 (d, δ 171.98, 1649, calcd for J = 5.2 Hz, 1H), 168.71, 1527, C₂₉H₃₃N₂O₇, 7.31-7.19 (m, 5H), 159.50, 1481, 521.2282; 7.14-7.05 (m, 4H), 155.37, 1327, found, 7.04-6.94 (m, 1H), 148.75, 1240, 521.2274 6.85 (d, J = 5.2 Hz, 1H), 140.57, 1207, 5.04 (dq, J = 9.6, 6.4 Hz, 138.13, 1059, 1H), 4.62 (dt, J = 10.8, 130.34, 1030, 7.6 Hz, 1H), 129.51, 752, 4.57-4.47 (m, 2H), 128.21, 549 4.42 (d, J = 11.5 Hz, 127.82, 1H), 3.92 (s, 3H), 127.56, 3.79-3.69 (m, 1H), 121.45, 2.41 (dt, J = 13.8, 6.6 Hz, 116.34, 1H), 109.54, 82.57, 2.31-2.13 (m, 1H), 82.49, 72.84, 1.98-1.63 (m, 2H), 71.68, 56.09, 1.51-1.30 (m, 4H), 1.09 (dd, J = 16.2, 51.32, 33.31, 7.3 Hz, 1H) 28.16, 18.41, 18.11 F24 Hard White 56-62 3367, HRMS-ESI ¹H NMR (CDCl₃) ¹³C NMR Foam 3030, (m/z) δ 12.06 (s, 1H), (CDCl₃) 2240, [M + H]⁺ 8.47 (d, J = 8.1 Hz, 1H), δ 171.95, 1743, calcd for 8.08-7.89 (m, 1H), 168.71, 1649, C₂₉H₃₃N₂O₇, 7.38-7.16 (m, 7H), 157.40, 1596, 521.2282; 7.03-6.91 (m, 3H), 155.37, 1327, found, 6.85 (d, J = 5.2 Hz, 148.75, 1240, 521.2282 1H), 4.97 (dq, J = 9.6, 140.56, 1211, 6.4 Hz, 1H), 137.91, 1061, 4.84 (d, J = 10.8 Hz, 1H), 130.34, 728, 4.75-4.57 (m, 2H), 129.63, 695 4.50 (t J = 5.4 Hz, 128.36, 1H), 3.93 (s, 3H), 128.23, 3.85 (dd, J = 9.6, 7.2 Hz, 127.82, 1H), 2.37 (dt, J = 13.6, 121.48, 7.0 Hz, 1H), 116.70, 2.29-2.12 (m, 1H), 109.52, 83.13, 1.94-1.78 (m, 1H), 82.91, 75.62, 1.68 (h, J = 8.0 Hz, 72.85, 56.09, 1H), 1.48 (d, J = 6.4 Hz, 51.25, 33.19, 3H), 28.29, 18.23, 1.44-1.29 (m, 1H), 1.09 (dd, J = 16.1, 18.15 7.8 Hz, 1H) F25 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Foam (m/z) 12.06 (s, 1H), (CDCl₃) δ [M + H]⁺ 8.48 (d, J = 8.1 Hz, 1H), 172.00, calcd for 7.99 (d, J = 5.2 Hz, 168.68, C₂₆H₃₅N₂O₇, 1H), 7.31-7.23 (m, 159.66, 487.2437; 2H), 7.08 (d, J = 7.8 Hz, 155.37, found, 2H), 6.95 (t, J = 7.3 Hz, 148.74, 487.2439 1H), 6.87 (d, 140.54, J = 5.2 Hz, 1H), 130.37, 5.03 (dq, J = 9.6, 6.4 Hz, 129.33, 1H), 4.62 (dt, J = 10.8, 121.31, 7.7 Hz, 1H), 116.41, 4.44 (dd, J = 9.6, 7.3 Hz, 109.50, 83.06, 1H), 3.94 (s, 3H), 82.76, 76.41, 3.55 (t, J = 5.5 Hz, 72.88, 56.08, 1H), 3.24 (dd, J = 8.7, 51.31, 33.37, 6.6 Hz, 1H), 28.71, 27.88, 3.06 (dd, J = 8.7, 6.2 Hz, 19.36, 19.21, 1H), 2.41 (dt, J = 13.8, 18.29, 18.11 6.6 Hz, 1H), 2.31-2.13 (m, 1H), 1.88-1.60 (m, 3H), 1.51-1.38 (m, 1H), 1.36 (d, J = 6.4 Hz, 3H), 1.04 (dd, J = 16.1, 7.3 Hz, 1H), 0.79 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.7 Hz, 3H) F26 — — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.62, calcd for 1H), 170.29, C₂₉H₃₈N₂NaO₉, 7.32-7.22 (m, 2H), 162.98, 581.2470; 7.13-7.02 (m, 2H), 160.28, found, 6.99-6.91 (m, 2H), 5.74 (s, 2H), 159.70, 581.2457 5.01 (dq, J = 9.6, 6.4 Hz, 145.73, 1H), 4.64 (dt, J = 10.8, 144.03, 7.6 Hz, 1H), 142.38, 4.43 (dd, J = 9.6, 7.3 Hz, 129.31, 1H), 3.91 (s, 3H), 121.25, 3.54 (t, J = 5.5 Hz, 116.42, 1H), 3.24 (dd, J = 8.8, 109.62 89.54, 6.6 Hz, 1H), 83.14, 82.82, 3.06 (dd, J = 8.8, 6.2 Hz, 76.39, 72.61, 1H), 2.42 (dt, J = 13.7, 56.19, 51.65, 6.7 Hz, 1H) 33.45, 28.70, 2.28-2.12 (m, 1H) 27.95, 20.88, 2.07 (s, 3H), 19.36, 19.21, 1.85-1.56 (m, 3H), 18.36, 18.10 1.45-1.29 (m, 4H), 1.04 (dd, J = 16.1, 7.5 Hz, 1H), 0.79 (d, J = 6.7 Hz, 3H), 0.73 (d, J = 6.7 Hz, 3H) F27 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.06 (d, J = 0.5 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.47 (d, J = 8.1 Hz, 171.96, calcd for 1H), 7.98 (d, J = 5.2 Hz, 168.68, C₂₆H₃₅N₂O₇, 1H), 157.54, 487.2439; 7.33-7.20 (m, 2H), 155.35, found, 7.01-6.89 (m, 3H), 6.86 (d, 148.72, 487.2438 J = 5.2 Hz, 1H), 140.53, 4.93 (dq, J = 9.7, 6.4 Hz, 130.35, 1H), 4.63 (dt, J = 10.8, 129.49, 7.6 Hz, 1H), 121.28, 4.39 (t, J = 5.4 Hz, 116.66, 1H), 3.94 (s, 3H), 109.48, 83.35, 3.64 (dd, J = 9.6, 7.2 Hz, 83.07, 80.68, 1H), 3.57 (dd, J = 8.6, 73.10, 56.07, 6.2 Hz, 1H), 51.24, 33.20, 3.40 (dd, J = 8.6, 6.6 Hz, 28.99, 28.17, 1H), 2.36 (dt, J = 13.6, 19.38, 19.28, 7.0 Hz, 1H), 18.19, 18.01 2.17 (tdd, J = 13.4, 6.4, 4.0 Hz, 1H), 1.89-1.55 (m, 3H), 1.47 (d, J = 6.4 Hz, 3H), 1.35 (q, J = 11.8, 11.4 Hz, 1H), 1.05 (dd, J = 16.1, 7.8 Hz, 1H), 0.83 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.7 Hz, 3H) F28 White 135-137 — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Powder (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.58, calcd for 1H), 170.28, C₂₉H₃₉N2O₉, 7.30-7.24 (m, 2H), 162.99, 559.2650; 6.98-6.89 (m, 4H), 5.74 (s, 2H), 160.27, found, 4.91 (dq, J = 9.7, 6.4 Hz, 157.60, 559.2652 1H), 4.65 (dt, J = 10.7, 145.73, 7.6 Hz, 1H), 144.00, 4.38 (t, J = 5.5 Hz, 142.36, 1H), 3.90 (s, 3H), 129.47, 3.63 (dd, J = 9.6, 7.2 Hz, 121.22, 1H), 3.57 (dd, J = 8.6, 116.68, 6.3 Hz, 1H), 109.62, 89.53, 3.40 (dd, J = 8.6, 6.7 Hz, 83.41, 83.16, 1H), 2.37 (dt, J = 13.6, 80.68, 72.83, 7.0 Hz, 1H), 56.19, 51.58, 2.24-2.09 (m, 1H), 33.30, 29.00, 2.07 (s, 3H), 28.26, 20.88, 1.87-1.56 (m, 3H), 1.46 (d, 19.39, 19.29, J = 6.4 Hz, 3H), 18.26, 18.00 1.30 (dd, J = 23.8, 10.8 Hz, 1H), 1.04 (dd, J = 16.1, 7.8 Hz, 1H), 0.83 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.7 Hz, 3H) F29 Sticky — 3378, HRMS-ESI ¹H NMR (CDCl₃) ¹³C NMR Yellow 2954, (m/z) δ 8.32 (d, J = 8.0 Hz, (CDCl₃) Solid 2872, [M + H]⁺ 1H), 8.27 (dd, J = 5.3, δ 172.64, 1745, calcd for 2.9 Hz, 1H), 170.25, 1676, C₂₇H₄₃N₂O₉, 6.95 (d, J = 5.4 Hz, 1H), 162.95, 1577, 539.2963; 5.74 (d, J = 2.6 Hz, 160.24, 1503, found, 2H), 4.80 (t, J = 6.5 Hz, 145.72, 1463, 539.2957 1H), 4.60 (dt, J = 10.4, 143.94, 1367, 7.8 Hz, 1H), 142.40, 1201, 3.91 (s, 3H), 109.60, 89.50, 1097, 3.62 (dd, J = 8.6, 6.2 Hz, 84.24, 83.71, 1058, 1H), 3.42-3.31 (m, 80.46, 75.78, 1003, 3H), 3.28 (dd, J = 8.6, 73.03, 56.17, 967, 6.5 Hz, 1H), 51.62, 33.38, 912, 3.12 (dd, J = 8.6, 6.3 Hz, 29.06, 28.87, 728 1H), 2.37 (dt, J = 13.6, 27.67, 20.85, 6.7 Hz, 1H), 19.55, 19.52, 2.21-2.09 (m, 1H), 19.37, 18.28, 2.07 (s, 3H), 17.97 1.82 (dtd, J = 13.0, 6.6, 3.6 Hz, 2H), 1.75-1.55 (m, 2H), 1.39 (d, J = 6.4 Hz, 3H), 1.35-1.21 (m, 1H), 0.97-0.85 (m, 13H) F30 Fluffy Light 42-52 3376, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Yellow 3030, (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) Solid 2939, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, δ 172.62, 2875, calcd for 1H), 170.29, 1745, C₃₃H₃₉N₂O₉, 7.40-7.23 (m, 10H), 6.94 (d, J = 5.4 Hz, 163.01, 1675, 607.2650; 1H), 5.74 (s, 160.28, 1577, found, 2H), 4.94-4.80 (m, 145.77, 1497, 607.2648 2H), 4.69 (d, J = 10.9 Hz, 143.99, 1453, 1H), 142.40, 1369, 4.67-4.57 (m, 2H), 4.49 (d, J = 11.4 Hz, 138.44, 1313, 1H), 3.89 (s, 138.37, 1200, 3H), 3.70-3.60 (m, 128.41, 1095, 2H), 2.40 (dt, J = 13.5, 128.38, 1058, 6.8 Hz, 1H), 127.95, 1002, 2.20 (dddd, J = 15.2, 127.82, 965, 12.4, 9.5, 4.4 Hz, 127.71, 828, 1H), 2.07 (s, 3H), 127.65, 736, 1.86-1.62 (m, 2H), 109.66, 89.53, 697 1.43 (d, J = 6.4 Hz, 83.96, 83.72, 3H), 1.40-1.29 (m, 75.75, 72.86, 1H), 1.08-0.95 (m, 71.20, 56.21, 1H) 51.66, 33.37, 28.03, 20.90, 18.41, 18.10 F31 Fluffy 49-55 3380, HRMS-ESI ¹H NMR (CDCl₃) ¹³C NMR White Solid 2941, (m/z) δ 8.33 (d, J = 8.0 Hz, (CDCl₃) 2877, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, δ 172.59, 1748, calcd for 1H), 170.30, 1676, C₃₂H₃₇N₂O₉, 7.33-7.18 (m, 5H), 163.01, 1585, 593.2494; 7.14-7.05 (m, 4H), 160.29, 1492, found, 7.05-6.85 (m, 2H), 5.74 (s, 2H), 159.53, 1368, 593.2499 5.02 (dq, J = 9.6, 6.4 Hz, 145.75, 1200, 1H), 4.64 (dt, J = 10.8, 144.03, 1130, 7.5 Hz, 1H), 142.34, 1030, 4.58-4.47 (m, 2H), 138.17, 1002, 4.47-4.36 (m, 1H), 129.49, 966, 3.90 (s, 3H), 128.19, 829, 3.78-3.66 (m, 1H), 127.81, 752, 2.42 (dt, J = 13.7, 6.7 Hz, 127.52, 694 1H), 2.29-2.13 (m, 121.39, 1H), 2.07 (s, 3H), 116.34, 1.89-1.64 (m, 2H), 109.66, 89.53, 1.44-1.30 (m, 4H), 82.62, 82.56, 1.08 (dd, J = 16.1, 72.57, 71.65, 7.5 Hz, 1H) 56.21, 51.66, 33.39, 28.22, 20.89, 18.47, 18.09 F32 Fluffy — 3379, HRMS-ESI ¹H NMR (CDCl₃) ¹³C NMR White Solid 2941, (m/z) δ 8.31 (d, J = 8.0 Hz, (CDCl₃) 1747, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, δ 172.55, 1676, calcd for 1H), 170.29, 1584, C₃₂H₃₇N₂O₉, 7.37-7.17 (m, 7H), 7.02-6.88 163.01, 1493, 593.2494; (m, 4H), 5.74 (s, 2H), 160.27, 1454, found, 4.95 (dq, J = 9.6, 6.3 Hz, 157.45, 1200, 593.2498 1H), 4.85 (d, J = 10.7 Hz, 145.75, 1061, 1H), 144.01, 1002, 4.74-4.61 (m, 2H), 4.49 (t, 142.34, 966, J = 5.5 Hz, 1H), 137.96, 829, 3.90 (s, 3H), 3.85 (dd, J = 9.6, 129.60, 753, 7.2 Hz, 1H), 128.34, 695 2.38 (dt, J = 13.6, 7.0 Hz, 128.22, 1H), 2.26-2.11 (m, 127.79, 1H), 2.07 (s, 3H), 121.41, 1.91-1.77 (m, 1H), 116.71, 1.66 (dd, J = 16.1, 109.65, 89.52, 7.8 Hz, 1H), 1.47 (d, 83.22, 83.00, J = 6.4 Hz, 3H), 75.63, 72.58, 1.37-1.23 (m, 1H), 56.20, 51.59, 1.08 (dd, J = 16.1, 7.8 Hz, 33.27, 28.37, 1H) 20.89, 18.30, 18.14 F33 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.16-12.07 (m, (CDCl₃) δ [M + Na]⁺ 1H), 8.48 (d, J = 8.1 Hz, 172.10, calcd for 1H), 7.98 (d, J = 5.2 Hz, 168.64, C₂₅H₃₈N₂NaO₇, 1H), 6.86 (d, 155.33, 501.2571; J = 5.2 Hz, 1H), 148.70, found, 4.76 (dq, J = 9.7, 6.4 Hz, 140.50, 501.2586 1H), 4.58 (dt, J = 10.8, 130.41, 7.7 Hz, 1H), 109.45, 84.23, 4.31 (d, J = 3.3 Hz, 83.14, 81.18, 1H), 3.94 (s, 3H), 75.92, 73.51, 3.54-3.42 (m, 1H), 56.06, 51.33, 3.32 (t, J = 5.6 Hz, 33.31, 32.94, 1H), 3.24 (dd, J = 8.6, 32.31, 28.90, 7.0 Hz, 1H), 27.59, 23.26, 3.15 (dd, J = 8.6, 6.0 Hz, 23.19, 19.63, 1H), 2.36 (dt, J = 13.7, 19.48, 18.27, 6.6 Hz, 1H), 18.13 2.25-2.08 (m, 1H), 1.90-1.50 (m, 11H), 1.44-1.30 (m, 4H), 0.92 (dd, J = 6.7, 4.8 Hz, 7H) F34 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) ¹³C NMR Solid (m/z) δ 8.39 (d, J = 8.0 Hz, (CDCl₃) [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, δ 176.25, calcd for 1H), 172.60, C₃₁H₄₃N₂O₉, 7.34-7.22 (m, 2H), 7.08 (d, J = 8.0 Hz, 162.96, 587.2963; 2H), 6.95 (t, J = 6.5 Hz, 160.25, found, 2H), 159.70, 587.3065 5.84-5.71 (m, 2H), 145.59, 5.01 (dq, J = 9.6, 6.4 Hz, 144.23, 1H), 4.64 (dt, J = 10.7, 142.03, 7.6 Hz, 1H), 129.31, 4.43 (dd, J = 9.6, 7.3 Hz, 121.25, 1H), 3.89 (s, 3H), 116.42, 3.54 (t, J = 5.6 Hz, 109.57, 89.88, 1H), 3.24 (dd, J = 8.7, 83.14, 82.82, 6.6 Hz, 1H), 76.38, 72.59, 3.06 (dd, J = 8.7, 6.3 Hz, 56.14, 51.65, 1H), 2.55 (p, J = 7.0 Hz, 33.85, 33.44, 1H), 2.42 (dt, J = 13.6, 28.70, 27.94, 6.7 Hz, 1H) 19.36, 19.21, 2.20 (dp, J = 15.7, 18.68, 18.36, 5.1 Hz, 1H), 18.09 1.86-1.61 (m, 3H), 1.45-1.31 (m, 4H), 1.14 (d, J = 7.0 Hz, 6H), 1.04 (dd, J = 16.1, 7.5 Hz, 1H), 0.79 (d, J = 6.7 Hz, 3H), 0.73 (d, J = 6.7 Hz, 3H) F35 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.25, calcd for 1H), 172.57, C₃₁H₄₃N₂O₉, 7.35-7.22 (m, 2H), 162.97, 587.2963; 7.01-6.87 (m, 4H), 160.25, found, 5.83-5.67 (m, 2H), 4.91 (dq, J = 9.7, 157.60, 587.2952 6.4 Hz, 1H), 145.59, 4.65 (dt, J = 10.7, 7.6 Hz, 144.22, 1H), 4.38 (t, J = 5.4 Hz, 142.02, 1H), 3.88 (s, 3H), 129.47, 3.63 (dd, J = 9.6, 7.2 Hz, 121.22, 1H), 3.57 (dd, J = 8.7, 116.67, 6.3 Hz, 1H), 109.55, 89.90, 3.40 (dd, J = 8.7, 6.7 Hz, 83.41, 83.16, 1H), 2.55 (p, J = 7.0 Hz, 80.68, 72.81, 1H), 2.36 (dt, J = 13.6, 56.13, 51.57, 7.0 Hz, 1H), 33.86, 33.31, 2.23-2.08 (m, 1H), 28.99, 28.25, 1.90-1.56 (m, 3H), 19.39, 19.29, 1.46 (d, J = 6.4 Hz, 18.68, 18.27, 3H), 1.36-1.27 (m, 18.00 1H), 1.14 (d, J = 7.0 Hz, 6H), 1.05 (dd, J = 16.1, 7.9 Hz, 1H), 0.83 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.7 Hz, 3H) F36 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.39 (d, J = 8.0 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.26, calcd for 1H), 172.53, C₃₃H₃₈N₂NaO₉, 7.29-7.15 (m, 4H), 162.99, 629.2470; 7.10-7.03 (m, 2H), 160.26, found, 6.98-6.88 (m, 3H), 159.53, 629.2460 6.88-6.82 (m, 2H), 157.59, 5.81-5.74 (m, 2H), 5.13 (dq, J = 9.6, 145.60, 6.4 Hz, 1H), 144.26, 4.67 (ddd, J = 9.6, 7.6, 3.1 Hz, 141.95, 2H), 129.43, 4.56-4.51 (m, 1H), 3.88 (s, 3H), 129.41, 121.61, 2.55 (p, J = 7.0 Hz, 121.52, 1H), 2.42 (dt, J = 13.6, 116.90, 7.1 Hz, 1H), 116.54, 2.35-2.21 (m, 1H), 109.60, 89.87, 1.98-1.85 (m, 1H), 82.45, 82.38, 1.74 (dt, J = 24.4, 8.1 Hz, 72.42, 56.15, 1H), 1.42 (d, J = 6.4 Hz, 51.60, 33.86, 3H), 1.36 (d, 33.29, 28.26, J = 13.1 Hz, 1H), 18.69, 18.37, 1.22-1.17 (m, 1H), 18.18 1.14 (d, J = 7.0 Hz, 6H) F37 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.24, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.65, C₂₉H₄₆N₂NaO₉, 1H), 162.93, 589.3096; 5.83-5.72 (m, 2H), 160.24, found, 4.79 (dq, J = 12.6, 6.2 Hz, 145.58, 589.3090 1H), 4.60 (dt, J = 10.7, 144.19, 7.6 Hz, 1H), 142.10, 3.89 (s, 3H), 109.52, 89.91, 3.62 (dd, J = 8.6, 6.2 Hz, 84.26, 83.74, 1H), 3.41-3.31 (m, 80.49, 75.81, 3H), 3.28 (dd, J = 8.6, 73.04, 56.12, 6.5 Hz, 1H), 51.63, 33.85, 3.12 (dd, J = 8.6, 6.3 Hz, 33.43, 29.08, 1H), 2.55 (p, J = 7.0 Hz, 28.88, 27.69, 1H), 2.37 (dt, J = 13.5, 19.57, 19.54, 6.7 Hz, 1H), 19.53, 19.39, 2.12 (ddt, J = 10.7, 18.67, 18.29, 8.2, 5.6 Hz, 1H), 17.98 1.90-1.54 (m, 4H), 1.39 (d, J = 6.4 Hz, 3H), 1.38-1.27 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.90 (t, J = 7.0 Hz, 13H) F38 Clear Tacky — — HRMS-ESI ¹NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.23, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.71, C₃₀H₄₆N₂NaO₉, 1H), 162.92, 601.3096; 5.83-5.72 (m, 2H), 160.23, found, 4.74 (dq, J = 9.6, 6.4 Hz, 145.58, 601.3105 1H), 4.60 (dt, J = 10.8, 144.18, 7.6 Hz, 1H), 142.12, 4.38-4.27 (m, 1H), 109.51, 89.90, 3.89 (s, 3H), 84.31, 83.13, 3.46 (dd, J = 9.6, 7.0 Hz, 81.25, 75.91, 1H), 3.31 (t, J = 5.5 Hz, 73.22, 56.12, 1H), 3.24 (dd, J = 8.6, 51.65, 33.85, 7.0 Hz, 1H), 33.42, 32.95, 3.14 (dd, J = 8.7, 6.0 Hz, 32.31, 28.89, 1H), 2.55 (hept, J = 7.0 Hz, 27.68, 23.26, 1H), 2.37 (dt, 23.18, 19.63, J = 13.6, 6.7 Hz, 1H), 19.49, 18.67, 2.17-2.06 (m, 1H), 18.34, 18.13 1.90-1.47 (m, 11H), 1.38 (d, J = 6.4 Hz, 3H), 1.32 (d, J = 11.3 Hz, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.92 (d, J = 4.5 Hz, 3H), 0.91 (d, J = 4.6 Hz, 3H), 0.88 (d, J = 7.5 Hz, 1H) F39 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.32 (d, J = 8.1 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.73, calcd for 1H), 6.94 (d, J = 5.4 Hz, 170.27, C₂₈H₄₃N₂O₉, 1H), 5.74 (s, 162.95, 551.2963; 2H), 4.74 (dq, J = 9.6, 160.26, found, 6.4 Hz, 1H), 145.72, 551.2962 4.60 (dt, J = 10.8, 7.5 Hz, 143.97, 1H), 4.31 (p, J = 5.3, 142.46, 4.6 Hz, 1H), 3.91 (s, 109.57, 89.55, 3H), 3.46 (dd, J = 9.6, 84.31, 83.13, 7.0 Hz, 1H), 81.25, 75.91, 3.31 (t, J = 5.5 Hz, 1H), 73.24, 56.18, 3.24 (dd, J = 8.6, 6.9 Hz, 51.66, 33.42, 1H), 3.14 (dd, J = 8.7, 32.95, 32.31, 6.0 Hz, 1H), 28.89, 27.68, 2.37 (dt, J = 13.6, 6.7 Hz, 23.26, 23.19, 1H), 2.07 (s, 4H), 20.87, 19.64, 1.89-1.46 (m, 11H), 19.49, 18.34, 1.38 (d, J = 6.4 Hz, 18.13 3H), 1.32 (d, J = 11.3 Hz, 1H), 0.92 (dd, J = 6.7, 4.6 Hz, 7H) F40 colorless — 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR semi solid 2949, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2870, [M + Na]⁺ 8.47 (d, J = 8.2 Hz, 1H), 172.04, 1742, calcd for 7.99 (d, J = 5.2 Hz, 168.62, 1650, C₂₉H₄₀N₂NaO₇, 1H), 7.33-7.23 (m, 155.38, 1528 551.2728; 2H), 7.23-7.13 (m, 148.73, found, 3H), 6.87 (d, J = 5.3 Hz, 142.02, 551.2734 1H), 140.49, 4.86-4.77 (m, 1H), 4.58 (dt, J = 10.8, 130.36, 7.6 Hz, 1H), 128.35, 3.94 (s, 3H), 3.85 (dt, 128.32, J = 9.1, 6.4 Hz, 1H), 125.77, 3.64 (dt, J = 9.1, 6.5 Hz, 109.45, 84.16, 1H), 83.85, 75.83, 3.43-3.32 (m, 2H), 3.27 (dd, J = 8.7, 73.19, 73.00, 6.6 Hz, 1H), 56.08, 51.31, 3.10 (dd, J = 8.7, 6.2 Hz, 33.31, 32.51, 1H), 2.68 (td, J = 7.6, 32.00, 28.86, 3.9 Hz, 2H), 27.62, 19.54, 2.43-2.30 (m, 1H), 19.48, 18.21, 2.21-2.08 (m, 1H), 18.02 1.96-1.84 (m, 2H), 1.78 (dq, J = 13.1, 6.5 Hz, 1H), 1.72-1.62 (m, 2H), 1.43-1.33 (m, 4H), 0.95-0.90 (m, 1H), 0.89 (dd, J = 6.7, 3.0 Hz, 6H) F41 White Solid 108-114 3370, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2955, (m/z) 12.07 (s, 1H), (CDCl₃) δ 2874, [M + Na]⁺ 8.47 (d, J = 8.2 Hz, 1H), 171.99, 1744, calcd for 7.99 (d, J = 5.2 Hz, 168.60, 1651, C₂₄H₃₅F₃N₂NaO₇, 1H), 6.87 (d, J = 5.2 Hz, 155.45, 1530, 543.2289; 1H), 4.80 (dq, J = 9.1, 148.77, 1263 found, 6.3 Hz, 1H), 140.45, δ 543.2291 4.58 (dt, J = 10.7, 7.6 Hz, 133.17-125.57 (m), 1H), 3.94 (s, 3H), 109.46, 83.99, 3.86 (dt, J = 9.2, 6.1 Hz, 83.96, 75.65, 1H), 3.68 (dt, J = 9.2, 72.93, 71.69, 6.3 Hz, 1H), 56.10, 51.31, 3.43-3.31 (m, 2H), 33.25, 3.28 (dd, J = 8.7, 6.7 Hz, 30.90 (q, J = 28.9 Hz), 1H), 3.09 (dd, J = 8.6, 28.88, 6.1 Hz, 1H), 27.39, 2.44-2.29 (m, 1H), 23.07 (q, J = 2.4 Hz), 2.26-2.09 (m, 3H), 19.54, 1.86-1.75 (m, 3H), 19.46, 18.16, 1.71-1.58 (m, 3H), 17.96 1.39 (d, J = 6.4 Hz, 3H), 0.97-0.85 (m, 7H) F42 White Solid 167-169 3387, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2955, (m/z) 8.50 (d, J = 8.3 Hz, (CDCl₃) δ 2877, [M + H]⁺ 1H), 8.33 (d, J = 5.5 Hz, 173.90, 1772, calcd for 1H), 7.00 (d, J = 5.4 Hz, 172.61, 1735, C₂₆H₃₇N₂O₉, 1H), 5.13 (dd, 168.93, 1679, 521.2494; J = 9.8, 7.8 Hz, 1H), 162.36, 1508, found, 4.95 (dq, J = 9.8, 6.4 Hz, 159.45, 1168 521.2505 1H), 4.63 (dt, J = 10.6, 146.66, 7.7 Hz, 1H), 141.39, 3.91 (s, 3H), 137.52, 3.37 (ddd, J = 7.6, 5.3, 1.9 Hz, 109.80, 81.19, 1H), 3.30 (dd, J = 8.8, 76.33, 75.64, 6.1 Hz, 1H), 71.49, 56.29, 2.98 (dd, J = 8.8, 6.8 Hz, 51.33, 33.64, 1H), 2.40 (s, 3H), 28.63, 28.12, 2.43-2.33 (m, 1H), 20.76, 19.32, 2.22-2.02 (m, 1H), 19.26, 18.03, 1.84-1.56 (m, 4H), 17.20, 12.88, 1.40-1.29 (m, 1H), 8.45, 8.38 1.28 (d, J = 6.4 Hz, 3H), 1.07-0.95 (m, 3H), 0.91-0.81 (m, 8H) F43 Colorless — 3389, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2950, (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ 2870, [M + H]⁺ 1H), 8.28 (d, J = 5.3 Hz, 172.68, 1750, calcd for 1H), 170.31, 1678, C₃₂H₄₅N₂O_(9,) 7.31-7.23 (m, 2H), 162.97, 1503, 601.3120; 7.22-7.14 (m, 3H), 6.94 (d, J = 5.4 Hz, 160.27, 1202 found, 1H), 5.74 (s, 145.73, 601.3136 2H), 4.84-4.75 (m, 144.00, 1H), 4.60 (dt, J = 10.7, 142.44, 7.6 Hz, 1H), 142.06, 3.91 (s, 3H), 3.85 (dt, 128.36, J = 9.1, 6.4 Hz, 1H), 128.33, 3.64 (dt, J = 9.2, 6.5 Hz, 125.77, 1H), 109.58, 99.98, 3.41-3.31 (m, 2H), 3.27 (dd, J = 8.8, 89.57, 84.25, 6.6 Hz, 1H), 83.91, 75.82, 3.09 (dd, J = 8.7, 6.3 Hz, 73.01, 72.93, 1H), 2.75-2.62 (m, 56.18, 51.63, 2H), 2.37 (dt, J = 13.5, 33.43, 32.52, 6.9 Hz, 1H), 32.02, 28.86, 2.17-2.07 (m, 1H), 27.70, 20.89, 2.07 (s, 3H), 19.54, 19.49, 1.94-1.83 (m, 2H), 18.28, 18.01 1.78 (dt, J = 13.2, 6.7 Hz, 1H), 1.70-1.58 (m, 2H), 1.40 (d, J = 6.3 Hz, 3H), 1.32 (q, J = 11.0 Hz, 1H), 0.95-0.89 (m, 1H), 0.89 (dd, J = 6.7, 2.9 Hz, 6H) F44 Colorless — 3382, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2954, (m/z) 8.31 (d, J = 8.1 Hz, (CDCl₃) δ 2875, [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.63, 1750, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.31, 1678, C₂₇H₄₀F₃N₂O₉, 1H), 5.74 (s, 162.98, 1504, 593.2680; 2H), 4.78 (dq, J = 9.3, 160.27, 1203 found, 6.4 Hz, 1H), 145.73, 593.2697 4.60 (dt, J = 10.8, 7.6 Hz, 144.01, 1H), 3.91 (s, 3H), 142.39, 3.85 (dt, J = 9.3, 6.1 Hz, 109.60, 89.55, 1H), 3.67 (dt, J = 9.3, 84.07, 84.01, 6.1 Hz, 1H), 75.63, 72.67, 3.42-3.30 (m, 2H), 71.68, 56.19, 3.27 (dd, J = 8.7, 6.6 Hz, 51.61, 1H), 3.09 (dd, J = 8.6, 30.91 (q, J = 29.1 Hz), 6.1 Hz, 1H), 28.87, 2.47-2.32 (m, 1H), 27.47, 23.09, 2.28-2.09 (m, 3H), 23.06, 20.89, 2.07 (s, 3H), 19.54, 19.46, 1.87-1.77 (m, 3H), 18.22, 17.95; 1.71-1.61 (m, 2H), 1.38 (d, J = 6.3 Hz, ¹⁹F NMR 3H), (CDCl₃) δ 1.37-1.23 (m, 1H), −66.38-−66.51 (m) 0.91 (dd, J = 6.8, 1.8 Hz, 6H), 0.89-0.85 (m, 1H) F45 Colorless — 3376, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2956, (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) δ 2873, [M + Na]⁺ 1H), 8.27 (dd, J = 5.5, 172.63, 1745, calcd for 1.5 Hz, 1H), 170.24, 1676, C₂₆H₄₀N₂NaO₉, 6.95 (d, J = 5.4 Hz, 1H), 162.95, 1502, 547.2626; 5.75-5.72 (m, 2H), 160.24, 1236 found, 4.78 (p, J = 6.8 Hz, 145.72, 547.2624 1H), 4.60 (dt, J = 11.0, 143.93, 7.6 Hz, 1H), 142.41, 3.91 (s, 3H), 3.78 (dt, 109.60, 89.49, J = 9.4, 6.6 Hz, 1H), 84.22, 83.76, 3.62-3.52 (m, 1H), 75.90, 75.39, 3.41-3.32 (m, 2H), 72.99, 56.17, 3.29 (dd, J = 8.7, 6.5 Hz, 51.62, 33.40, 1H), 28.85, 27.75, 3.16-3.10 (m, 1H), 2.37 (dt, J = 13.5, 23.50, 20.85, 6.8 Hz, 1H), 19.50, 19.47, 2.18-2.09 (m, 1H), 18.27, 17.88, 2.07 (s, 3H), 10.67 1.82 (hept, J = 6.6 Hz, 1H), 1.71-1.53 (m, 4H), 1.40 (d, J = 6.5 Hz, 3H), 1.38-1.22 (m, 1H), 0.97-0.85 (m, 10H) F46 Colorless — 3378, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2954, (m/z) 8.37-8.23 (m, 2H), (CDCl₃) δ 2873, [M + Na]⁺ 6.95 (d, J = 5.4 Hz, 173.90, 1732, calcd for 1H), 5.74 (s, 2H), 172.72, 1676, C₂₇H₃₈N₂NaO₁₀, 5.15 (dd, J = 9.8, 7.8 Hz, 170.32, 1501, 573.2419; 1H), 4.96 (dq, J = 9.6, 162.96, 1163 found, 6.4 Hz, 1H), 160.29, 573.2415 4.63 (dt, J = 10.7, 7.5 Hz, 145.69, 1H), 3.91 (s, 3H), 144.10, 3.38 (ddt, J = 7.6, 142.34, 5.4, 3.0 Hz, 1H), 109.61, 89.58, 3.30 (dd, J = 8.8, 6.1 Hz, 76.33, 75.67, 1H), 2.98 (dd, J = 8.8, 71.49, 56.19, 6.8 Hz, 1H), 51.64, 33.41, 2.40 (dt, J = 13.8, 7.3 Hz, 28.65, 28.13, 1H), 2.15 (dddd, J = 15.8, 20.88, 19.32, 10.1, 8.0, 5.4 Hz, 19.27, 18.08, 1H), 2.07 (s, 3H), 17.23, 12.89, 1.77 (dt, J = 13.3, 6.7 Hz, 8.44, 8.37 2H), 1.72-1.56 (m, 2H), 1.43-1.32 (m, 1H), 1.29 (d, J = 6.4 Hz, 3H), 1.08-0.99 (m, 3H), 0.90-0.84 (m, 8H) F47 Yellow- — 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi Solid 2956, (m/z) 8.56-8.48 (m, 1H), (CDCl₃) δ 2874, [M + H]⁺ 8.33 (d, J = 5.4 Hz, 172.55, 1772, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.92, 1744, C₂₅H₃₉N₂O₈, 1H), 4.78 (t, J = 7.7 Hz, 162.38, 1679, 495.2701; 1H), 4.59 (dt, 159.42, 1508, found, J = 10.7, 7.7 Hz, 1H), 146.69, 1198 495.2713 3.91 (s, 3H), 3.77 (dt, 141.43, J = 8.8, 6.5 Hz, 1H), 137.47, 3.56 (dt, J = 8.9, 6.8 Hz, 109.77, 84.25, 1H), 83.77, 75.95, 3.42-3.31 (m, 2H), 3.28 (dd, J = 8.8, 75.44, 73.04, 6.4 Hz, 1H), 56.28, 51.35, 3.12 (dd, J = 8.8, 6.3 Hz, 28.86, 27.77, 1H), 2.40 (s, 3H), 23.52, 20.76, 2.38-2.26 (m, 1H), 19.52, 19.49, 2.17-2.05 (m, 1H), 18.23, 17.87, 1.81 (dt, J = 13.2, 6.6 Hz, 10.68 1H), 1.72-1.56 (m, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.36-1.19 (m, 2H), 1.02-0.81 (m, 10H) F48 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR m/z 616.2 8.33 (d, J = 7.9 Hz, (CDCl₃) δ−122.28, ([M + H]⁺) 1H), 8.28 (d, J = 5.4 Hz, −122.60 1H), 7.03-6.87 (m, 7H), 6.82-6.75 (m, 2H), 5.74 (s, 2H), 5.10 (dq, J = 9.7, 6.4 Hz, 1H), 4.68 (dt, J = 10.7, 7.5 Hz, 1H), 4.53 (dd, J = 9.6, 7.4 Hz, 1H), 4.40 (ddd, J = 7.3, 5.2, 1.8 Hz, 1H), 3.91 (s, 3H), 2.43 (dt, J = 13.8, 7.0 Hz, 1H), 2.29-2.16 (m, 1H), 2.07 (s, 3H), 1.95-1.81 (m, 1H), 1.81-1.68 (m, 1H), 1.42 (d, J = 6.4 Hz, 3H), 1.41-1.28 (m, 1H), 1.23-1.10 (m, 1H) F49 White Solid — — ESIM ¹H NMR (CDCl₃) δ ¹⁹F NMR m/z 643.2 8.38 (d, J = 8.0 Hz, (CDCl₃) δ−122.29, ([M + H]⁺) 1H), 8.27 (d, J = 5.3 Hz, −122.61 1H), 7.03-6.86 (m, 7H), 6.82-6.76 (m, 2H), 5.80-5.74 (m, 2H), 5.10 (dq, J = 9.5, 6.3 Hz, 1H), 4.68 (dt, J = 10.8, 7.6 Hz, 1H), 4.53 (dd, J = 9.6, 7.3 Hz, 1H), 4.40 (ddd, J = 7.3, 5.2, 1.8 Hz, 1H), 3.89 (s, 3H), 2.55 (p, J = 7.0 Hz, 1H), 2.42 (dt, J = 13.9, 7.1 Hz, 1H), 2.22 (dddd, J = 15.8, 10.3, 7.9, 5.2 Hz, 1H), 1.94-1.82 (m, 1H), 1.80-1.67 (m, 1H), 1.42 (d, J = 6.4 Hz, 3H), 1.40-1.33 (m, 1H), 1.33-1.26 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H) F50 White Solid 89-91 3364, HRMS ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2918, (m/z) 12.04 (s, 1H), (CDCl₃) δ 1745, calcd for 8.49 (d, J = 8.1 Hz, 1H), 171.92, 1649, C₂₈H₂₈F₂N₂O₇, 7.98 (d, J = 5.2 Hz, 168.81, 1502, 542.1865; 1H), 7.05-6.75 (m, 157.81 (d, J = 239.9 Hz), 1200 found, 9H), 5.11 (dq, J = 9.6, 155.66 (d, J = 2.0 Hz), 542.1872 6.3 Hz, 1H), 155.44, 4.67 (dt, J = 10.8, 7.6 Hz, 154.63 (d, J = 208.1 Hz), 1H), 4.54 (dd, J = 9.5, 153.60 (d, J = 2.0 Hz), 7.4 Hz, 1H), 148.82, 4.41 (ddd, J = 7.1, 5.2, 1.8 Hz, 140.65, 1H), 3.93 (s, 3H), 130.31, 2.42 (dt, J = 13.7, 7.2 Hz, 118.35 (d, J = 8.0 Hz), 1H), 117.77 (d, J = 8.2 Hz), 2.31-2.16 (m, 1H), 116.05 (d, J = 6.3 Hz), 1.96-1.82 (m, 1H), 115.82 (d, J = 6.6 Hz), 1.85-1.68 (m, 1H), 109.63, 83.67, 1.47-1.36 (m, 1H), 1.43 (d, J = 6.3 Hz, 83.43, 72.51, 3H), 56.14, 51.27, 1.16 (ddt, J = 15.9, 7.6, 33.22, 28.20, 1.8 Hz, 1H) 18.33, 18.23 F51 Colorless — 3376, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2954, (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ 2875, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.27, 1746, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.62, 1679, C₂₉H₄₄F₃N₂O₉, 1H), 162.95, 1504, 621.2993; 5.85-5.67 (m, 2H), 160.26, 1253, found, 4.78 (dq, J = 9.2, 6.3 Hz, 145.60, 1100, 621.3003 1H), 4.60 (dt, J = 10.8, 144.23, 833 7.6 Hz, 1H), 142.05, 3.89 (s, 3H), 109.54, 89.92, 3.87-3.81 (m, 1H), 84.08, 84.02, 3.68 (dt, J = 9.2, 6.3 Hz, 75.63, 72.65, 1H), 3.41-3.31 (m, 71.69, 56.14, 2H), 3.28 (dd, J = 8.7, 51.61, 33.86, 6.6 Hz, 1H), 33.39, 3.09 (dd, J = 8.7, 6.2 Hz, 30.91 (q, J = 28.7 Hz), 1H), 2.55 (hept, J = 7.0 Hz, 28.88, 1H), 27.47, 2.37 (dtd, J = 13.6, 6.6, 23.08 (q, J = 2.4 Hz), 1.7 Hz, 1H), 19.55, 2.26-2.06 (m, 3H), 19.47, 18.69, 1.86-1.76 (m, 3H), 18.23, 17.95; 1.75-1.56 (m, 2H), 1.38 (d, ¹⁹F NMR J = 6.3 Hz, 3H), (CDCl₃) δ 1.35-1.25 (m, 1H), −66.43 (t, J = 11.0 Hz) 1.14 (d, J = 7.0 Hz, 6H), 0.91 (dd, J = 6.7, 1.8 Hz, 6H), 0.93-0.86 (m, 1H) F52 Colorless — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2955, (m/z) 8.36 (d, J = 7.9 Hz, (CDCl₃) δ 2874, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.29, 1736, calcd for 1H), 6.95 (d, J = 5.3 Hz, 173.90, 1678, C₂₉H₄₃N₂O₁₀, 1H), 172.72, 1503, 579.2912; 5.81-5.72 (m, 2H), 162.92, 1383, found, 5.15 (dd, J = 9.8, 7.8 Hz, 160.26, 1315, 579.2922 1H), 4.96 (dq, J = 9.7, 145.55, 1165, 6.4 Hz, 1H), 144.31, 1094, 4.63 (dt, J = 10.6, 7.5 Hz, 141.99, 1027, 1H), 3.89 (s, 3H), 109.53, 89.94, 973 3.38 (ddd, J = 7.6, 81.20, 76.32, 5.4, 1.9 Hz, 1H), 75.66, 71.46, 3.31 (dd, J = 8.8, 6.1 Hz, 56.13, 51.63, 1H), 2.99 (dd, J = 8.8, 33.86, 33.40, 6.8 Hz, 1H), 28.64, 28.11, 2.55 (hept, J = 7.0 Hz, 19.32, 19.27, 1H), 2.44-2.29 (m, 18.69, 18.07, 1H), 2.23-2.05 (m, 17.22, 12.88, 1H), 1.84-1.56 (m, 8.45, 8.38 4H), 1.44-1.29 (m, 1H), 1.29 (d, J = 6.4 Hz, 3H), 1.14 (d, J = 7.0 Hz, 6H), 1.07-0.98 (m, 3H), 0.92-0.83 (m, 8H) F53 Colorless — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid (m/z) 12.07 (s, 1H), (CDCl₃) δ [M + H]⁺ 8.48 (d, J = 8.2 Hz, 1H), 171.97, calcd for 7.98 (d, J = 5.2 Hz, 168.68, C₂₄H₃₄F₃N₂O₇, 1H), 6.87 (d, J = 5.2 Hz, 155.36, 519.2313; 1H), 6.43 (dtt, J = 13.6, 148.73, found, 4.0, 2.0 Hz, 140.55, 519.2324 1H), 5.90 (dqt, J = 15.3, 136.86 (q, J = 6.3 Hz), 6.6, 2.2 Hz, 130.35, 1H), 4.86 (dq, J = 9.4, 123.14 (q, J = 269.1 Hz), 6.3 Hz, 1H), 118.09 (q, J = 34.1 Hz), 4.60 (dt, J = 10.7, 7.6 Hz, 109.50, 84.27, 1H), 4.54-4.45 (m, 83.94, 75.68, 1H), 4.34-4.25 (m, 72.65, 71.03, 1H), 3.94 (s, 3H), 56.08, 51.26, 3.46 (dd, J = 9.4, 7.2 Hz, 33.26, 28.84, 1H), 27.44, 19.49, 3.44-3.36 (m, 1H), 3.28 (dd, J = 8.7, 19.40, 18.16, 6.6 Hz, 1H), 17.96; 3.09 (dd, J = 8.7, 6.1 Hz, ¹⁹F NMR 1H), 2.44-2.31 (m, (CDCl₃) δ −64.24 1H), 2.24-2.09 (m, 1H), 1.88-1.75 (m, 1H), 1.75-1.59 (m, 2H), 1.41 (d, J = 6.3 Hz, 3H), 1.40-1.30 (m, 1H), 0.98-0.93 (m, 1H), 0.90 (dd, J = 6.7, 3.3 Hz, 6H) F54 Colorless — 3369, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2946, (m/z) 12.03 (s, 1H), (CDCl₃) δ 1747, [M]⁺ 8.47 (d, J = 8.1 Hz, 1H), 172.01, 1651, calcd for 7.99 (d, J = 5.2 Hz, 168.85, 1504, C₂₉H₃₁FN₂O₈, 1H), 7.07-7.01 (m, 157.85 (d, J = 239.3 Hz), 1203 554.2064; 2H), 6.98-6.90 (m, 155.90 (d, J = 2.2 Hz), found, 2H), 6.87 (d, J = 5.2 Hz, 155.52, 554.2074 1H), 154.80, 6.84-6.74 (m, 4H), 5.11 (dq, J = 9.6, 151.52, 6.4 Hz, 1H), 148.89, 4.66 (dt, J = 10.8, 7.7 Hz, 140.70, 1H), 4.53 (dd, J = 9.6, 130.44, 7.4 Hz, 1H), 118.68, 4.36 (ddd, J = 7.2, 5.2, 1.8 Hz, 117.96 (d, J = 7.9 Hz), 1H), 3.94 (s, 3H), 115.95 (d, J = 23.0 Hz), 3.74 (s, 3H), 2.42 (dt, 114.74, J = 13.8, 7.3 Hz, 1H), 109.67, 84.07, 2.24 (dddd, J = 15.8, 83.69, 72.67, 10.3, 8.0, 5.1 Hz, 56.23, 55.78, 1H), 1.96-1.84 (m, 51.36, 33.39, 1H), 1.84-1.72 (m, 28.18, 18.44, 1H), 1.44-1.34 (m, 18.35; 1H), 1.43 (d, J = 6.4 Hz, ¹⁹F NMR 3H), 1.12 (ddt, J = 16.2, (CDCl₃) δ −122.66 7.8, 1.8 Hz, 1H) F55 Colorless 65-67 2953, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid 2873, (m/z) 12.06 (s, 1H), (CDCl₃) δ 1746, [M]⁺ 8.48 (d, J = 8.1 Hz, 1H), 171.95, 1651, calcd for 7.99 (d, J = 5.1 Hz, 168.69, 1503, C₂₆H₃₃FN₂O₇, 1H), 7.07-7.01 (m, 157.52 (d, J = 238.6 Hz), 1201 504.2272; 2H), 6.99-6.92 (m, 156.33, found, 2H), 6.87 (d, J = 5.2 Hz, 155.87 (d, J = 2.2 Hz), 504.2282 1H), 5.02 (dq, J = 9.6, 155.35, 6.4 Hz, 1H), 148.73, 4.62 (dt, J = 10.7, 7.6 Hz, 140.54, 1H), 4.32 (dd, J = 9.6, 130.32, 7.3 Hz, 1H), 117.56 (d, J = 8.0 Hz), 3.94 (s, 3H), 3.54 (ddd, J = 7.1, 115.63 (d, J = 23.0 Hz), 5.2, 1.7 Hz, 109.51, 83.79, 1H), 3.25 (dd, J = 8.7, 83.04, 76.24, 6.6 Hz, 1H), 72.70, 56.07, 3.05 (dd, J = 8.7, 6.1 Hz, 51.28, 33.30, 1H), 2.47-2.35 (m, 28.71, 27.69, 1H), 2.22 (dddd, J = 15.8, 19.37, 19.23, 10.0, 8.4, 5.3 Hz, 18.24, 18.12; 1H), ¹⁹F NMR 1.83-1.64 (m, 3H), (CDCl₃) δ −123.24 1.50-1.39 (m, 1H), 1.36 (d, J = 6.4 Hz, 3H), 1.03 (ddt, J = 16.0, 6.7, 1.9 Hz, 1H), 0.80 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H) F56 Off-White 131-133 3369, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid 2954, (m/z) 12.05 (s, 1H), (CDCl₃) δ 1743, [M]⁺ 8.46 (d, J = 8.2 Hz, 1H), 171.92, 1650, calcd for 7.98 (d, J = 5.2 Hz, 168.69, 1503, C₂₆H₃₃FN₂O₇, 1H), 7.00-6.92 (m, 157.56 (d, J = 239.2 Hz), 1202 504.2272; 2H), 6.91-6.84 (m, 155.36, found, 3H), 4.92 (dq, J = 9.6, 153.66 (d, J = 2.5 Hz), 504.2294 6.4 Hz, 1H), 148.73, 4.63 (dt, J = 10.7, 7.6 Hz, 140.54, 1H), 4.27 (ddd, J = 7.1, 130.34, 5.3, 1.8 Hz, 1H), 117.95 (d, J = 7.8 Hz), 3.94 (s, 3H), 115.89 (d, J = 23.3 Hz), 3.65-3.52 (m, 2H), 109.50, 84.24, 3.41 (dd, J = 8.6, 6.6 Hz, 83.32, 80.79, 1H), 2.43-2.31 (m, 73.06, 56.08, 1H), 2.12 (dddd, J = 15.8, 51.22, 33.22, 10.2, 7.9, 5.3 Hz, 29.03, 28.18, 1H), 19.39, 19.31, 1.88-1.60 (m, 3H), 1.47 (d, J = 6.3 Hz, 18.19, 17.96; 3H), ¹⁹F NMR 1.42-1.29 (m, 1H), (CDCl₃) δ −122.87 1.04 (ddt, J = 16.1, 7.8, 1.9 Hz, 1H), 0.85 (d, J = 6.7 Hz, 3H), 0.81 (d, J = 6.7 Hz, 3H) F57 Flaky White — 3366, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid 2953, (m/z) 12.07 (d, J = 0.6 Hz, (CDCl₃) δ 2872, [M + Na]⁺ 1H), 8.48 (d, J = 8.2 Hz, 171.99, 1745, calcd for 1H), 8.00 (d, J = 5.1 Hz, 168.66, 1506, C₂₇H₃₆N₂NaO₈, 1H), 155.36, 1208 539.2364; 7.09-6.98 (m, 2H), 6.87 (d, 154.19, found, J = 5.2 Hz, 1H), 153.96, 539.2365 6.84-6.78 (m, 2H), 148.74, 5.01 (dq, J = 9.5, 6.4 Hz, 140.53, 1H), 4.61 (dt, J = 10.8, 130.38, 7.6 Hz, 1H), 117.54, 4.29 (dd, J = 9.6, 7.2 Hz, 114.42, 1H), 3.95 (s, 3H), 109.48, 83.93, 3.78 (s, 3H), 83.07, 76.38, 3.54 (ddd, J = 7.2, 5.2, 1.7 Hz, 72.97, 56.08, 1H), 3.25 (dd, J = 8.8, 55.69, 51.30, 6.7 Hz, 1H), 33.38, 28.74, 3.09 (dd, J = 8.8, 6.2 Hz, 27.79, 19.42, 1H), 2.50-2.34 (m, 19.28, 18.27, 1H), 2.28-2.12 (m, 18.18 1H), 1.84-1.66 (m, 3H), 1.49-1.38 (m, 1H), 1.37 (d, J = 6.4 Hz, 3H), 1.03 (dd, J = 16.1, 6.9 Hz, 1H), 0.80 (dd, J = 18.7, 6.7 Hz, 6H) F58 Purple — 3381, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2956, (m/z) 8.57-8.47 (m, 1H), (CDCl₃) δ 2875, [M + Na]⁺ 8.34 (d, J = 5.4 Hz, 172.46, 1773, calcd for 1H), 7.01 (d, J = 5.5 Hz, 168.91, 1745, C₂₆H₃₅F₃N₂NaO₈, 1H), 162.40, 1680, 583.2238; 6.56-6.36 (m, 1H), 159.44, 1510, found, 5.99-5.79 (m, 1H), 146.69, 1119 583.2244 4.91-4.73 (m, 1H), 141.37, 4.66-4.54 (m, 1H), 137.50, 4.53-4.40 (m, 1H), 136.91, 4.34-4.15 (m, 1H), 3.91 (s, 3H), 118.22, 3.50-3.35 (m, 2H), 117.88, 3.28 (dd, J = 8.7, 6.6 Hz, 109.81, 84.33, 1H), 3.08 (dd, J = 8.7, 84.01, 75.68, 6.2 Hz, 1H), 72.39, 71.02, 2.40 (s, 3H), 56.29, 51.31, 2.38-2.31 (m, 1H), 33.57, 28.82, 2.23-2.06 (m, 1H), 1.80 (dp, J = 13.2, 27.54, 20.75, 6.7 Hz, 1H), 19.48, 19.40, 1.69-1.59 (m, 3H), 18.18, 17.93; 1.38 (d, J = 6.3 Hz, ¹⁹F NMR 3H), 1.36-1.26 (m, (CDCl₃) δ −64.22 1H), 0.89 (dd, J = 6.6, 2.6 Hz, 6H) F59 Light — 3381, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Yellow 2955, (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ Semi-Solid 2875, [M + Na]⁺ 1H), 8.28 (d, J = 5.3 Hz, 172.59, 1748, calcd for 1H), 6.95 (d, J = 5.5 Hz, 170.31, 1678, C₂₇H₃₇F₃N₂NaO₉, 1H), 162.99, 1504, 613.2343; 6.42 (ddq, J = 15.7, 4.0, 160.28, 1310, found, 2.1 Hz, 1H), 145.74, 1115 613.2349 5.95-5.84 (m, 1H), 5.74 (s, 144.02, 2H), 4.84 (dq, J = 9.3, 142.37, 6.3 Hz, 1H), 136.93, 4.61 (dt, J = 10.8, 7.6 Hz, 117.89, 1H), 4.55-4.44 (m, 109.61, 89.55, 1H), 4.29 (dt, J = 15.3, 84.35, 84.02, 4.1 Hz, 1H), 76.70, 75.67, 3.91 (s, 3H), 72.38, 71.03, 3.45 (dd, J = 9.5, 7.2 Hz, 56.19, 51.60, 1H), 3.41-3.35 (m, 33.36, 28.83, 1H), 3.28 (dd, J = 8.7, 27.52, 20.89, 6.6 Hz, 1H), 19.49, 19.41, 3.08 (dd, J = 8.7, 6.2 Hz, 18.23, 17.95; 1H), 2.38 (dt, J = 13.5, ¹⁹F NMR 6.7 Hz, 1H), (CDCl₃) δ 2.21-2.10 (m, 1H), −64.23 (p, J = 3.3 Hz) 2.08 (s, 3H), 1.80 (dt, J = 13.2, 6.6 Hz, 1H), 1.71-1.60 (m, 2H), 1.39 (d, J = 6.3 Hz, 3H), 1.37-1.29 (m, 1H), 0.98-0.88 (m, J = 7.3 Hz, 1H), 0.90 (dd, J = 6.7, 3.0 Hz, 6H) F60 Yellow Oil — 3384, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2946, (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) δ 1751, [M]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.61, 1677, calcd for 1H), 170.42, 1502, C₃₂H₃₅FN₂O₁₀, 7.07-7.01 (m, 2H), 163.14, 1200, 626.2276; 6.97-6.89 (m, 3H), 160.42, 1035 found, 6.83-6.73 (m, 4H), 5.74 (s, 2H), 157.82 (d, J = 239.1 Hz), 626.2306 5.09 (dq, J = 9.5, 6.4 Hz, 155.93 (d, J = 2.7 Hz), 1H), 4.67 (dt, J = 10.8, 154.76, 7.6 Hz, 1H), 151.58, 4.52 (dd, J = 9.6, 7.4 Hz, 145.86, 1H), 4.35 (ddd, J = 7.2, 144.19, 5.2, 1.8 Hz, 142.40, 1H), 3.91 (s, 3H), 3.74 (s, 3H), 2.42 (dt, J = 13.8, 7.0 Hz, 1H), 118.68, 2.30-2.15 (m, 1H), 117.96 (d, J = 8.0 Hz), 2.07 (s, 3H), 115.92 (d, J = 23.0 Hz), 1.96-1.82 (m, 1H), 114.73, 1.82-1.68 (m, 1H), 1.42 (d, 109.80, 89.65, J = 6.4 Hz, 3H), 84.15, 83.75, 1.41-1.31 (m, 1H), 72.40, 56.33, 1.11 (ddt, J = 16.2, 8.2, 55.77, 51.72, 1.8 Hz, 1H) 33.45, 28.26, 21.01, 18.51, 18.34; ¹⁹F NMR (CDCl₃) δ−122.77 F61 Yellow Oil — 3384, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ 1750, [M]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.57, 1678, calcd for 1H), 170.29, 1503, C₂₉H₃₇FN₂O₉, 7.06-7.00 (m, 2H), 162.99, 1200 576.2483; 6.99-6.92 (m, 3H), 5.74 (s, 2H), 160.28, found 5.00 (dq, J = 9.6, 6.4 Hz, 157.51 (d, J = 238.8 Hz), 576.2508 1H), 4.63 (dt, J = 10.8, 155.91 (d, J = 2.2 Hz), 7.6 Hz, 1H), 145.73, 4.31 (dd, J = 9.6, 7.3 Hz, 144.03, 1H), 3.91 (s, 3H), 142.35, 3.53 (ddd, J = 7.2, 117.56 (d, J = 8.0 Hz), 5.2, 1.7 Hz, 1H), 115.62 (d, J = 22.9 Hz), 3.25 (dd, J = 8.8, 6.6 Hz, 109.65, 89.52, 1H), 3.04 (dd, J = 8.8, 83.86, 83.13, 6.2 Hz, 1H), 76.24, 72.44, 2.47-2.32 (m, 1H), 56.20, 51.64, 2.20 (dddd, J = 15.6, 10.4, 33.39, 28.72, 8.3, 5.3 Hz, 1H), 27.78, 20.87, 2.07 (s, 3H), 19.37, 19.23, 1.83-1.61 (m, 3H), 18.32, 18.12; 1.43-1.33 (m, 1H), 1.35 (d, J = 6.4 Hz, ¹⁹F NMR 3H), (CDCl₃) δ−123.37 1.02 (ddt, J = 16.0, 7.2, 1.9 Hz, 1H), 0.80 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H) F62 Yellow Oil — 3381, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 8.38 (d, J = 8.0 Hz, (CDCl₃) δ 1747, [M]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.26, 1678, calcd for 1H), 172.57, 1503, C₃₁H₄₁FN₂O₉, 7.06-7.01 (m, 2H), 162.96, 1201 604.2796; 6.98-6.92 (m, 3H), 160.26, found, 5.80-5.73 (m, 2H), 5.00 (dq, J = 9.6, 157.51 (d, J = 238.8 Hz), 604.2811 6.4 Hz, 1H), 155.91 (d, J = 2.2 Hz), 4.63 (dt, J = 10.8, 7.6 Hz, 145.59, 1H), 4.31 (dd, J = 9.6, 144.25, 7.3 Hz, 1H), 142.02, 3.89 (s, 3H), 3.53 (ddd, J = 7.1, 117.57 (d, J = 8.0 Hz), 5.2, 1.7 Hz, 115.62 (d, J = 23.1 Hz), 1H), 3.25 (dd, J = 8.8, 109.58, 89.88, 6.6 Hz, 1H), 83.87, 83.13, 3.04 (dd, J = 8.8, 6.2 Hz, 76.25, 72.43, 1H), 2.54 (h, J = 7.0 Hz, 56.14, 51.63, 1H), 33.86, 33.41, 2.46-2.36 (m, 1H), 2.20 (dddd, 28.72, 27.78, J = 11.3, 10.0, 8.4, 19.37, 19.24, 5.2 Hz, 1H), 18.68, 18.33, 1.85-1.59 (m, 3H), 18.12; 1.43-1.33 (m, 1H), 1.35 (d, ¹⁹F NMR J = 6.4 Hz, 3H), (CDCl₃) δ−123.38 1.14 (d, J = 7.0 Hz, 6H), 1.03 (ddt, J = 16.5, 7.7, 2.1 Hz, 1H), 0.80 (d, J = 6.7 Hz, 3H), 0.75 (d, J = 6.7 Hz, 3H); F63 Off-White 139-141 3371, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid 2959, (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ 1747, [M]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.54, 1676, calcd for 1H), 170.28, 1503, C₂₉H₃₇FN₂O₉, 7.00-6.90 (m, 3H), 163.00, 1202 576.2483; 6.92-6.84 (m, 2H), 5.74 (s, 2H), 160.27, found, 4.89 (dq, J = 9.7, 6.4 Hz, 157.54 (d, J = 239.0 Hz), 576.2489 1H), 4.65 (dt, J = 10.8, 153.71 (d, J = 2.2 Hz), 7.6 Hz, 1H), 145.73, 4.26 (ddd, J = 7.2, 144.01, 5.3, 1.7 Hz, 1H), 142.34, 3.91 (s, 3H), 117.96 (d, J = 8.0 Hz), 3.67-3.49 (m, 2H), 3.40 (dd, J = 8.6, 115.86 (d, J = 23.1 Hz), 6.6 Hz, 1H), 109.63, 89.52, 2.42-2.29 (m, 1H), 84.32, 83.38, 2.07 (s, 3H), 80.77, 72.79, 1.88-1.55 (m, 3H), 1.45 (d, J = 6.4 Hz, 56.19, 51.56, 3H), 33.30, 29.02, 1.37-1.22 (m, 2H), 28.26, 20.88, 1.03 (ddt, J = 16.0, 7.8, 19.39, 19.31, 1.8 Hz, 1H), 0.84 (d, 18.25, 17.95; J = 6.7 Hz, 3H), ¹⁹F NMR 0.81 (d, J = 6.7 Hz, 3H) (CDCl₃) δ−122.98 F64 Colorless 84-86 3366, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid 2949, (m/z) 12.05 (s, 1H), (CDCl₃) δ 1649, [M]⁺ 8.48 (d, J = 8.1 Hz, 1H), 171.90, 1505, calcd for 7.98 (d, J = 5.2 Hz, 168.71, 1212, C₃₀H₃₄N₂O₉, 1H), 7.07-6.98 (m, 155.36, 566.2264; 2H), 6.89-6.71 (m, 154.60, found, 7H), 5.09 (dq, J = 9.6, 154.43, 566.2281 6.4 Hz, 1H), 153.86, 4.65 (dt, J = 10.8, 7.6 Hz, 151.58, 1H), 4.50 (dd, J = 9.5, 148.75, 7.3 Hz, 1H), 140.56, 4.36 (ddd, J = 7.2, 5.1, 1.7 Hz, 130.31, 1H), 3.93 (s, 3H), 118.65, 3.75 (s, 3H), 3.73 (s, 117.80, 3H), 2.41 (dt, J = 13.8, 114.58, 7.0 Hz, 1H), 114.53, 2.29-2.14 (m, 1H), 109.54 84.08, 1.97-1.83 (m, 1H), 83.63, 72.76, 1.83-1.69 (m, 1H), 56.08, 55.64, 1.45 (d, J = 6.4 Hz, 51.24, 33.27, 3H), 1.45-1.34 (m, 28.06, 18.31, 1H), 1.10 (ddt, J = 16.4, 18.27, 14.21 7.9, 1.8 Hz, 1H) F65 Colorless 70-72 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid 2953, (m/z) 12.07 (s, 1H), (CDCl₃) δ 1742, [M]⁺ 8.47 (d, J = 8.1 Hz, 1H), 171.95, 1649, calcd for 7.97 (d, J = 5.2 Hz, 168.68, 1504, C₂₇H₃₆N₂O₈, 1H), 6.92-6.80 (m, 155.33, 1213 516.2472; 5H), 4.91 (dq, J = 9.6, 154.36, found, 6.3 Hz, 1H), 151.44, 516.2483 4.63 (dt, J = 10.8, 7.6 Hz, 148.71, 1H), 4.23 (ddd, J = 7.0, 140.53, 5.1, 1.7 Hz, 1H), 130.33, 3.93 (s, 3H), 3.76 (s, 118.25, 3H), 3.66-3.56 (m, 114.62, 2H), 3.41 (dd, J = 8.6, 109.50, 84.59, 6.6 Hz, 1H), 83.30, 80.75, 2.36 (dt, J = 13.6, 7.3 Hz, 73.11, 56.07, 1H), 2.12 (dddd, J = 15.8, 55.65, 51.23, 10.3, 7.9, 5.1 Hz, 33.24, 29.06, 1H), 28.03, 19.45, 1.88-1.74 (m, 2H), 19.36, 18.20, 1.76-1.59 (m, 1H), 18.00 1.47 (d, J = 6.4 Hz, 3H), 1.40-1.28 (m, 1H), 0.98 (ddt, J = 16.2, 8.1, 1.7 Hz, 1H), 0.87 (d, J = 6.6 Hz, 3H), 0.84 (d, J = 6.7 Hz, 3H) F66 Yellow Oil — 3384, ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR 2959, (m/z) 640.3 8.33 (d, J = 8.0 Hz, (CDCl₃) δ 1750, ([M + 2H]⁺) 1H), 8.27 (d, J = 5.3 Hz, 172.52, 1677, 1H), 170.30, 1504, 7.07-6.99 (m, 2H), 6.95 (d, J = 5.4 Hz, 163.01, 1203 1H), 160.28, 1036 6.86-6.72 (m, 6H), 5.74 (s, 154.56, 2H), 5.08 (dq, J = 9.5, 154.39, 6.3 Hz, 1H), 153.90, 4.67 (dt, J = 10.7, 7.6 Hz, 151.63, 1H), 4.49 (dd, J = 9.6, 145.74, 7.3 Hz, 1H), 144.03, 4.35 (ddd, J = 7.3, 5.2, 1.7 Hz, 142.29, 1H), 3.90 (s, 3H), 118.68, 3.75 (s, 3H), 3.73 (s, 117.80, 3H), 2.42 (dt, J = 13.8, 114.56, 7.0 Hz, 1H), 114.52, 2.22 (dddd, J = 15.8, 109.67, 89.51, 10.3, 8.0, 5.3 Hz, 84.18, 83.70, 1H), 2.07 (s, 3H), 72.50, 56.20, 1.94-1.82 (m, 1H), 55.66, 51.60, 1.82-1.68 (m, 1H), 33.35, 28.13, 1.43 (d, J = 6.4 Hz, 20.89, 18.39, 3H), 1.40-1.28 (m, 18.26 1H), 1.10 (ddt, J = 16.2, 7.9, 1.9 Hz, 1H) F67 Yellow Oil — 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2944, (m/z) 8.38 (d, J = 8.0 Hz, (CDCl₃) δ 1747, [M]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.27, 1678, calcd for 1H), 172.52, 1505, C₃₅H₄₂N₂O₁₁, 7.07-6.99 (m, 2H), 6.94 (d, J = 5.4 Hz, 162.98, 1214, 666.2789; 1H), 160.26, 1036 found, 6.86-6.73 (m, 6H), 154.57, 666.2793 5.80-5.74 (m, 2H), 154.39, 5.08 (dq, J = 9.5, 6.4 Hz, 153.91, 1H), 4.67 (dt, J = 10.7, 151.64, 7.6 Hz, 1H), 145.60, 4.49 (dd, J = 9.6, 7.4 Hz, 144.26, 1H), 4.35 (ddd, J = 7.2, 141.97, 5.1, 1.7 Hz, 118.68, 1H), 3.89 (s, 3H), 117.81, 3.75 (s, 3H), 3.74 (s, 114.56, 3H), 2.62-2.47 (m, 114.52, 1H), 2.42 (dt, J = 13.8, 109.59, 89.88, 7.0 Hz, 1H), 84.19, 83.71, 2.22 (dddd, J = 15.7, 72.49, 56.15, 9.9, 7.9, 5.2 Hz, 1H), 55.65, 51.59, 1.95-1.82 (m, 1H), 33.86, 33.37, 1.81-1.69 (m, 1H), 28.14, 18.69, 1.43 (d, J = 6.4 Hz, 18.40, 18.27 3H), 1.43-1.29 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 1.13-1.04 (m, 1H) F68 White Solid 118-120 3376, ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR 2956, m/z 589.3 8.31 (d, J = 8.0 Hz, (CDCl₃) δ 1751, ([M + H]⁺) 1H), 8.27 (d, J = 5.3 Hz, 172.56, 1679, 1H), 6.94 (d, J = 5.4 Hz, 170.28, 1506, 1H), 162.99, 6.91-6.86 (m, 2H), 160.26, 6.85-6.78 (m, 2H), 5.74 (s, 154.33, 2H), 4.89 (dq, J = 9.6, 151.50, 6.3 Hz, 1H), 145.73, 4.65 (dt, J = 10.8, 7.6 Hz, 143.99, 1H), 4.23 (ddd, J = 7.0, 142.35, 5.2, 1.7 Hz, 1H), 118.27, 3.90 (s, 3H), 3.77 (s, 114.60, 3H), 3.68-3.55 (m, 109.63, 89.52, 2H), 3.41 (dd, J = 8.7, 84.69, 83.36, 6.6 Hz, 1H), 80.75, 72.84, 2.37 (dt, J = 13.7, 7.0 Hz, 56.19, 55.65, 1H), 2.16-2.07 (m, 51.57, 33.35, 1H), 2.07 (s, 3H), 29.06, 28.09, 1.80 (dtt, J = 13.3, 20.88, 19.45, 8.5, 4.6 Hz, 2H), 19.36, 18.26, 1.73-1.55 (m, 1H), 18.00 1.45 (d, J = 6.3 Hz, 3H), 1.35-1.22 (m, 1H), 0.98 (ddt, J = 16.1, 7.9, 1.7 Hz, 1H), 0.87 (d, J = 6.7 Hz, 3H), 0.83 (d, J = 6.7 Hz, 3H) F69 Yellow Oil — 3383, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2956, (m/z) 8.36 (d, J = 8.0 Hz, (CDCl₃) δ 1747, [M]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.24, 1678, calcd for 1H), 6.93 (d, J = 5.4 Hz, 172.55, 1506, C₃₂H₄₄N₂O₁₀, 1H), 162.96, 1216 616.2996; 6.91-6.86 (m, 2H), 160.24, found, 6.85-6.79 (m, 2H), 154.32, 616.3006 5.80-5.74 (m, 2H), 151.50, 4.89 (dq, J = 9.6, 6.3 Hz, 145.59, 1H), 4.64 (dt, J = 10.7, 144.20, 7.6 Hz, 1H), 142.01, 4.27-4.19 (m, 1H), 118.26, 3.88 (s, 3H), 3.77 (s, 114.60, 3H), 3.64-3.57 (m, 109.56, 89.89, 2H), 3.41 (dd, J = 8.7, 84.69, 83.36, 6.6 Hz, 1H), 80.75, 72.83, 2.55 (hept, J = 7.0 Hz, 56.14, 55.65, 1H), 2.37 (dt, J = 13.7, 51.56, 33.85, 7.0 Hz, 1H), 33.36, 29.06, 2.10 (dddd, J = 15.7, 28.09, 19.45, 10.2, 8.0, 5.1 Hz, 19.36, 18.68, 1H), 1.87-1.73 (m, 18.27, 17.99 2H), 1.72-1.57 (m, 1H), 1.45 (d, J = 6.3 Hz, 3H), 1.35-1.22 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.98 (ddt, J = 16.2, 7.6, 1.7 Hz, 1H), 0.87 (d, J = 6.7 Hz, 3H), 0.83 (d, J = 6.7 Hz, 3H) F70 White Semi- — 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid 2955, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2872, [M + H]⁺ 8.47 (d, J = 8.0 Hz, 1H), 172.05, 1744, calcd for 7.99 (d, J = 5.2 Hz, 168.65, 1650, C₂₅H₄₁N₂O₇, 1H), 6.87 (d, J = 5.2 Hz, 155.34, 1529 481.2908; 1H), 4.79 (dp, J = 9.6, 148.71, found, 6.1 Hz, 1H), 140.51, 481.2922 4.58 (dt, J = 10.8, 7.6 Hz, 130.41, 1H), 3.94 (s, 3H), 109.45, 84.17, 3.81 (dt, J = 9.0, 6.6 Hz, 83.78, 75.97, 1H), 3.60 (dt, J = 8.9, 73.89, 73.30, 6.7 Hz, 1H), 56.07, 51.30, 3.43-3.33 (m, 2H), 33.35, 30.06, 3.28 (dd, J = 8.7, 6.5 Hz, 28.88, 28.39, 1H), 3.13 (dd, J = 8.7, 27.69, 22.57, 6.3 Hz, 1H), 19.54, 19.48, 2.44-2.32 (m, 1H), 18.22, 17.91, 2.21-2.07 (m, 1H), 14.05 1.81 (dq, J = 13.2, 6.6 Hz, 1H), 1.75-1.63 (m, 2H), 1.61-1.51 (m, 2H), 1.41 (t, J = 6.5 Hz, 3H), 1.39-1.24 (m, 4H), 1.00-0.80 (m, 11H) F71 Colorless — 3365, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2953, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2873, [M + H]⁺ 8.47 (d, J = 8.2 Hz, 1H), 172.06, 1744, calcd for 7.99 (d, J = 5.2 Hz, 168.65, 1650, C₂₅H₄₁N₂O₈, 1H), 6.87 (d, J = 5.3 Hz, 155.35, 1529, 497.2857; 1H), 4.80 (ddd, J = 8.5, 148.72, 1482 found, 6.2, 2.4 Hz, 140.51, 497.2864 1H), 4.58 (dt, J = 10.7, 130.40, 7.7 Hz, 1H), 109.46, 84.10, 3.94 (s, 3H) 83.90, 83.84, 3.93-3.81 (m 1H), 75.86, 74.16, 3.79-3.63 (m, 1H), 73.68, 73.20, 3.52-3.23 (m, 7H), 73.13, 70.40, 3.13 (dt, J = 8.7, 6.3 Hz, 70.09, 56.08, 1H), 2.41-2.32 (m, 56.01, 55.96, 1H), 2.21-2.05 (m, 51.30, 37.38, 1H), 1.92-1.60 (m, 37.28, 33.33, 5H), 1.47-1.36 (m, 28.88, 27.65, 4H), 1.15 (dd, J = 6.1, 19.54, 19.48, 2.1 Hz, 3H), 19.15, 19.12, 0.96-0.86 (m, 7H) 18.21, 17.97, 17.93 F72 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2952, (m/z) 8.31 (d, J = 8.2 Hz, (CDCl₃) δ 2873, [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.67, 1747, calcd for 1H), 6.95 (d, J = 5.3 Hz, 170.30, 1678, C₂₈H₄₅N₂O₁₀, 1H), 5.74 (s, 162.96, 1504, 569.3069; 2H), 4.78 (dqt, J = 10.4, 160.26, 1202, found, 6.5, 3.3 Hz, 145.74, 1099 569.3093 1H), 4.60 (dt, J = 10.7, 143.99, 7.6 Hz, 1H), 142.42, 3.91 (s, 3H), 109.58, 89.55, 3.89-3.80 (m, 1H), 84.18, 83.95, 3.77-3.71 (m, 1H), 83.89, 75.84, 3.66 (dt, J = 9.2, 6.6 Hz, 74.17, 73.70, 1H), 3.50-3.24 (m, 72.93, 72.86, 8H), 3.12 (dt, J = 8.8, 70.39, 70.08, 6.3 Hz, 1H), 56.18, 56.00, 2.43-2.33 (m, 1H), 55.96, 51.63, 2.19-2.09 (m, 1H), 2.07 (s, 37.38, 37.28, 3H), 1.88-1.73 (m, 33.42, 28.87, 2H), 1.72-1.55 (m, 27.72, 20.88, 5H), 1.35-1.28 (m, 19.55, 19.49, 1H), 1.15 (dd, J = 6.1, 19.14, 19.12, 2.1 Hz, 3H), 18.27, 17.96, 0.92 (dd, J = 6.7, 1.9 Hz, 17.92 6H), 0.89-0.81 (m, 1H) F73 White Solid 61-63 3368, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 12.09 (s, 1H), (CDCl₃) δ 1743, [M]⁺ 8.50 (d, J = 8.2 Hz, 1H), 172.10, 1650, calcd for 7.96 (d, J = 5.3 Hz, 168.62, 1529, C₂₆H₃₈N₂O₇, 1H), 6.86 (d, J = 5.2 Hz, 155.22, 1265 490.2679; 1H), 4.74 (dp, J = 12.9, 148.60, found, 6.4 Hz, 1H), 140.46, 490.2708 4.58 (dt, J = 10.8, 7.6 Hz, 130.28, 1H), 109.42, 83.24, 4.37-4.29 (m, 1H), 81.67, 80.96, 4.06-3.97 (m, 1H), 3.94 (s, 3H), 78.88, 73.66, 3.46-3.32 (m, 2H), 55.99, 51.27, 2.42-2.27 (m, 1H), 33.50, 33.24, 2.09 (dtd, J = 17.1, 32.73, 32.41, 7.8, 6.0, 3.2 Hz, 1H), 31.68, 23.69, 1.86-1.44 (m, 19H), 23.46, 23.38, 1.40 (d, J = 6.4 Hz, 23.31, 23.28, 3H), 0.90 (dd, J = 16.2, 18.50, 18.06 7.2 Hz, 1H) F74 White Solid 91-93 3365, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2953, (m/z) 12.08 (s, 1H), (CDCl₃) δ 1745, [M]⁺ 8.50 (d, J = 8.0 Hz, 1H), 172.01, 1650, calcd for 7.98 (d, J = 5.2 Hz, 168.68, 1529, C₂₇H₃₄N₂O₇, 1H), 7.30-7.21 (m, 159.76, 1492, 498.2366; 2H), 7.11-7.03 (m, 155.33, 1209 found, 2H), 6.98-6.90 (m, 148.71, 498.2355 1H), 6.86 (d, J = 5.2 Hz, 140.53, 1H), 5.02 (dq, J = 9.7, 130.32, 6.5 Hz, 1H), 129.26, 4.62 (dt, J = 10.8, 7.6 Hz, 121.18, 1H), 4.40 (dd, J = 9.5, 116.23, 7.3 Hz, 1H), 109.50, 82.55, 3.99-3.92 (m, 1H), 80.49, 79.68, 3.93 (s, 3H), 72.93, 56.06, 3.66-3.58 (m, 1H), 51.31, 33.37, 2.47-2.31 (m, 1H), 33.33, 31.76, 2.25-2.09 (m, 1H), 28.45, 23.40, 1.91-1.37 (m, 9H), 1.36 (d, J = 6.3 Hz, 22.96, 18.55, 3H), 18.12 1.33-1.17 (m, 2H), 1.04 (dd, J = 16.1, 7.3 Hz, 1H) F75 White Solid 68-70 3368, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 12.07 (s, 1H), (CDCl₃) δ 1744, [M]⁺ 8.48 (d, J = 8.1 Hz, 1H), 172.02, 1650, calcd for 7.97 (d, J = 5.2 Hz, 168.69, 1530, C₂₇H₃₄N₂O₇, 1H), 7.31-7.22 (m, 157.57, 1482, 498.2366; 2H), 6.98-6.89 (m, 155.33, 1241 found, 3H), 6.85 (d, J = 5.2 Hz, 148.71, 498.2360 1H), 4.89 (dq, J = 9.6, 140.53, 6.4 Hz, 1H), 130.33, 4.63 (dt, J = 10.8, 7.6 Hz, 129.50, 1H), 4.38-4.30 (m, 121.21, 1H), 4.27 (tt, J = 5.3, 116.52, 3.6 Hz, 1H), 3.93 (s, 109.50, 83.74, 3H), 3.74 (dd, J = 9.6, 82.77, 80.97, 7.1 Hz, 1H), 73.29, 56.06, 2.41-2.28 (m, 1H), 51.27, 33.16, 2.25-2.09 (m, 1H), 32.89, 32.42, 1.90-1.76 (m, 1H), 28.09, 23.11, 1.76-1.48 (m, 8H), 18.22, 18.09 1.46 (d, J = 6.4 Hz, 3H), 1.44-1.28 (m, 2H), 1.03 (ddt, J = 16.2, 7.9, 1.8 Hz, 1H) F76 Thick — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Yellow Oil 2954, (m/z) 8.38 (d, J = 8.1 Hz, (CDCl₃) δ 1745, [M]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.21, 1678, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.75, 1504, C₃₁H₄₆N₂O₉, 1H), 162.92, 1209 590.3203; 5.81-5.73 (m, 2H), 160.23, found, 4.73 (dq, J = 8.7, 6.4 Hz, 145.58, 590.3216 1H), 4.60 (dt, J = 10.7, 144.18, 7.5 Hz, 1H), 142.09, 4.33 (ddd, J = 7.9, 109.52, 89.90, 4.2, 2.2 Hz, 1H), 83.28, 81.82, 4.02 (qd, J = 5.6, 4.1 Hz, 81.08, 78.94, 1H), 3.89 (s, 3H), 73.43, 56.12, 3.46-3.36 (m, 2H), 51.65, 33.84, 2.55 (hept, J = 7.0 Hz, 33.53, 33.47, 1H), 2.37 (dtd, J = 13.6, 32.78, 32.44, 6.8, 1.7 Hz, 31.74, 28.39, 1H), 2.16-2.01 (m, 23.71, 23.41, 1H), 1.85-1.44 (m, 23.34, 23.31, 18H), 1.38 (d, J = 6.4 Hz, 18.66, 18.60, 3H), 1.32 (dt, J = 10.8, 18.09 2.3 Hz, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.90 (ddt, J = 16.3, 7.5, 1.9 Hz, 1H) F77 White Solid 73-75 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2953, (m/z) 8.53 (d, J = 7.8 Hz, (CDCl₃) δ 1772, [M]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.65, 1679, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.87, 1508, C₂₈H₄₀N₂O₈, 1H), 4.72 (dq, 162.37, 1198 532.2785; J = 8.1, 6.2 Hz, 1H), 159.42, found, 4.58 (ddd, J = 10.8, 146.68, 532.2807 8.4, 7.3 Hz, 1H), 141.43, 4.32 (qd, J = 5.0, 3.3 Hz, 137.47, 1H), 4.01 (qd, J = 5.4, 109.78, 83.30, 3.6 Hz, 1H), 81.85, 81.07, 3.90 (s, 3H), 78.97, 73.46, 3.46-3.34 (m, 2H), 2.40 (s, 3H), 56.28, 51.38, 2.39-2.30 (m, 1H), 33.67, 33.52, 2.14-2.01 (m, 1H), 32.80, 32.45, 1.85-1.43 (m, 18H), 31.75, 28.41, 1.37 (d, J = 6.4 Hz, 23.72, 23.41, 3H), 1.34-1.26 (m, 23.34, 23.31, 1H), 0.95-0.83 (m, 20.74, 18.57, 1H) 18.08 F78 Pale Yellow — 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2951, (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ 1749, [M]⁺ 1H), 8.28 (d, J = 5.3 Hz, 172.65, 1677, calcd for 1H), 170.30, 1493, C₃₀H₃₈N₂O₉, 7.30-7.22 (m, 2H), 162.98, 1201 570.2577; 7.10-7.04 (m, 2H), 160.28, found, 6.98-6.90 (m, 2H), 159.80, 570.2584 5.77-5.71 (m, 2H), 5.00 (dq, J = 9.6, 145.73, 6.4 Hz, 1H), 144.03, 4.64 (dt, J = 10.8, 7.6 Hz, 142.37, 1H), 4.39 (dd, J = 9.6, 129.25, 7.4 Hz, 1H), 121.13, 3.95 (tt, J = 5.4, 3.4 Hz, 116.25, 1H), 3.91 (s, 3H), 109.62, 89.55, 3.61 (ddd, J = 7.2, 82.62, 80.59, 5.2, 1.8 Hz, 1H), 79.69, 72.70, 2.42 (dtd, J = 13.6, 6.8, 56.19, 51.66, 1.6 Hz, 1H), 33.47, 33.36, 2.25-2.09 (m, 1H), 2.07 (s, 31.77, 28.55, 3H), 1.86-1.49 (m, 23.40, 22.97, 5H), 1.49-1.35 (m, 20.88, 18.63, 5H), 1.34 (d, J = 6.4 Hz, 18.12 3H), 1.35-1.29 (m, 1H), 1.03 (ddt, J = 15.9, 7.6, 2.0 Hz, 1H) F79 Pale Yellow — 3375, ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2944, m/z 599.3 8.38 (d, J = 8.1 Hz, (CDCl₃) δ 1745, ([M + H]⁺) 1H), 8.27 (d, J = 5.3 Hz, 176.26, 1676, 1H), 172.64, 1492, 7.30-7.23 (m, 2H), 162.95, 1205 7.10-7.03 (m, 2H), 160.26, 6.97-6.91 (m, 2H), 159.80, 5.81-5.73 (m, 2H), 5.01 (dq, J = 9.6, 145.59, 6.4 Hz, 1H), 144.24, 4.63 (dt, J = 10.8, 7.6 Hz, 142.04, 1H), 4.39 (dd, J = 9.6, 129.25, 7.4 Hz, 1H), 121.13, 3.95 (tt, J = 5.4, 3.4 Hz, 116.25, 1H), 3.89 (s, 3H), 109.56, 89.90, 3.61 (ddd, J = 7.2, 82.64, 80.59, 5.2, 1.8 Hz, 1H), 79.68, 72.68, 2.55 (hept, J = 7.0 Hz, 56.14, 51.65, 1H), 2.42 (dtd, J = 13.6, 33.86, 33.48, 6.8, 1.6 Hz, 33.37, 31.77, 1H), 2.24-2.09 (m, 28.55, 23.40, 1H), 1.85-1.49 (m, 22.97, 18.68, 5H), 1.49-1.35 (m, 18.63, 18.12 5H), 1.34 (d, J = 6.4 Hz, 3H), 1.34-1.28 (m, 1H), 1.14 (d, J = 7.1 Hz, 6H), 1.04 (ddt, J = 15.9, 7.5, 1.9 Hz, 1H) F80 White Solid 148-149 3373, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2952, (m/z) 8.31 (d, J = 8.1 Hz, (CDCl₃) δ 1749, [M]⁺ 1H), 8.27 (d, J = 5.3 Hz, 172.64, 1677, calcd for 1H), 170.29, 1494, C₃₀H₃₈N₂O₉, 7.31-7.23 (m, 2H), 162.99, 1202 570.2577; 6.99-6.89 (m, 4H), 5.74 (s, 2H), 160.26, found, 4.87 (dq, J = 9.6, 6.4 Hz, 157.62, 570.2577 1H), 4.65 (dt, J = 10.8, 145.73, 7.6 Hz, 1H), 143.99, 4.33 (ddd, J = 7.0, 142.36, 5.2, 1.7 Hz, 1H), 129.48, 4.26 (td, J = 5.3, 2.8 Hz, 121.16, 1H), 3.90 (s, 3H), 116.55, 3.74 (dd, J = 9.6, 7.1 Hz, 109.62, 89.52, 1H), 2.36 (dt, J = 13.7, 83.74, 82.87, 7.0 Hz, 1H), 81.03, 73.03, 2.24-2.09 (m, 1H), 56.19, 51.61, 2.07 (s, 3H), 33.28, 32.89, 1.89-1.75 (m, 1H), 32.42, 28.16, 1.75-1.45 (m, 7H), 1.45 (d, 23.11, 20.88, J = 6.4 Hz, 3H), 18.29, 18.09 1.45-1.36 (m, 2H), 1.35-1.25 (m, 1H), 1.03 (ddt, J = 16.0, 7.7, 1.8 Hz, 1H) F81 Thick — 3373, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Colorless 2952, (m/z) 8.53 (d, J = 8.4 Hz, (CDCl₃) δ Oil 1746, [M]⁺ 1H), 8.34 (d, J = 5.4 Hz, 172.53, 1679, calcd for 1H), 168.90, 1493, C₂₉H₃₆N₂O₈, 7.30-7.22 (m, 2H), 162.40, 1198 540.2472; 7.09-7.03 (m, 2H), 7.00 (d, J = 5.5 Hz, 159.79, found, 1H), 159.45, 540.2464 6.97-6.92 (m, 1H), 146.69, 5.00 (dq, J = 9.7, 6.4 Hz, 141.41, 1H), 4.68-4.57 (m, 137.52, 1H), 4.37 (dd, J = 9.7, 129.26, 7.4 Hz, 1H), 121.13, 3.98-3.92 (m, 1H), 116.26, 3.91 (s, 3H), 3.60 (ddd, J = 7.3, 109.81, 82.62, 5.2, 1.8 Hz, 80.60, 79.70, 1H), 2.40 (s, 3H), 72.71, 56.29, 2.24-2.07 (m, 1H), 51.37, 33.36, 1.83-1.49 (m, 6H), 31.77, 28.57, 1.49-1.34 (m, 5H), 23.40, 22.96, 1.33 (d, J = 6.4 Hz, 20.75, 18.59, 3H), 1.34-1.28 (m, 18.10, 14.21 1H); 1.07-0.99 (m, 1H) F82 Colorless — 3367, HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, Semi-Solid 2954, (m/z) CDCl₃) δ 12.06 (s, CDCl₃) 2872, [M + Na]⁺ 1H), 8.48 (d, J = 8.1 Hz, δ 172.00, 1744, calcd for 1H), 8.00 (d, J = 5.2 Hz, 168.67, 1650, C₂₇H₃₆N₂NaO₇, 1H), 7.06 (d, 157.65, 1508, 523.2415; J = 8.6 Hz, 2H), 155.37, 1207 found, 6.98 (d, J = 8.6 Hz, 2H), 148.75, 523.2409 6.87 (d, J = 5.3 Hz, 140.53, 1H), 5.01 (dq, J = 9.5, 130.57, 6.4 Hz, 1H), 130.39, 4.61 (dt, J = 10.8, 7.7 Hz, 129.79, 1H), 4.37 (dd, J = 9.6, 116.32, 7.3 Hz, 1H), 109.49, 83.12, 3.94 (s, 3H), 3.54 (ddd, J = 7.2, 83.04, 76.45, 5.3, 1.7 Hz, 73.00, 56.08, 1H), 3.24 (dd, J = 8.8, 51.31, 33.39, 6.6 Hz, 1H), 28.73, 27.90, 3.08 (dd, J = 8.8, 6.2 Hz, 20.50, 19.40, 1H), 2.41 (dt, J = 13.7, 19.25, 18.29, 6.6 Hz, 1H), 18.12 2.29 (s, 3H), 2.27-2.16 (m, 1H), 1.87-1.66 (m, 3H), 1.47-1.37 (m, 1H), 1.35 (d, J = 6.4 Hz, 3H), 1.07-0.99 (m, 1H), 0.81 (d, J = 6.7 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H) F83 Brownish — 3380, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2952, (m/z) 8.52 (d, J = 8.9 Hz, (CDCl₃) δ 2873, [M + H]⁺ 1H), 8.33 (d, J = 5.3 Hz, 172.54, 1771, calcd for 1H), 7.00 (d, J = 5.2 Hz, 168.91, 1743, C₂₇H₄₃N₂O₉, 1H), 162.38, 1677, 539.2963; 4.77 (ddd, J = 8.8, 6.0, 2.5 Hz, 159.43, 1506, found, 1H), 4.59 (dt, J = 10.6, 146.69, 1195 539.2984 7.8 Hz, 1H), 141.40, 3.90 (s, 3H), 137.48, 3.89-3.79 (m, 1H), 109.79, 84.19, 3.76-3.61 (m, 1H), 84.17, 84.11, 3.49-3.21 (m, 7H), 83.93, 83.87, 3.12 (dt, J = 8.8, 6.3 Hz, 75.85, 74.17, 1H), 2.40 (s, 3H), 73.69, 72.93, 2.38-2.30 (m, 1H), 72.87, 70.38, 2.17-2.02 (m, 1H), 70.06, 56.29, 1.91-1.48 (m, 5H), 56.00, 55.95, 1.42-1.35 (m, 3H), 51.35, 37.38, 1.30 (dtd, J = 13.8, 37.28, 33.61, 11.5, 2.0 Hz, 1H), 28.86, 27.73, 1.15 (dd, J = 6.1, 2.0 Hz, 20.75, 19.54, 3H), 19.49, 19.14, 0.95-0.88 (m, 6H), 0.87 (d, J = 7.7 Hz, 19.12, 18.23, 1H) 17.94, 17.90 F84 White Solid — 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 12.01 (s, 1H), (CDCl₃) δ 2871, [M + H]⁺ 8.46 (d, J = 8.1 Hz, 1H), 175.81, 1737, calcd for 7.99 (d, J = 5.2 Hz, 175.51, 1650, C₂₈H₃₉N₂O₉, 1H), 6.87 (d, J = 5.2 Hz, 171.83, 1529, 547.2650; 1H), 5.28 (dd, J = 9.8, 168.69, 1157 found, 8.1 Hz, 1H), 155.37, 547.2637 5.12-5.04 (m, 1H), 148.73, 5.01 (ddd, J = 7.8, 5.4, 2.2 Hz, 140.56, 1H), 4.66 (dt, J = 10.8, 130.28, 7.6 Hz, 1H), 109.52, 74.66, 3.94 (s, 3H), 73.70, 71.42, 2.77-2.58 (m, 2H), 56.09, 51.16, 2.47-2.35 (m, 1H), 43.87, 43.78, 2.16 (dddd, J = 15.9, 10.1, 33.12, 30.09, 7.8, 5.4 Hz, 1H), 30.00, 29.94, 1.93-1.79 (m, 5H), 29.80, 29.16, 1.78-1.63 (m, 9H), 25.77, 25.70, 1.62-1.51 (m, 4H), 18.11, 17.24 1.49-1.35 (m, 1H), 1.31 (d, J = 6.4 Hz, 3H), 1.19 (ddt, J = 16.4, 7.9, 2.3 Hz, 1H) F85 White Solid — 3368, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2946, (m/z) 12.05 (s, 1H), (CDCl₃) δ 2882, [M + H]⁺ 8.46 (d, J = 8.1 Hz, 1H), 171.93, 1744, calcd for 7.99 (d, J = 5.2 Hz, 168.69, 1650, C₂₄H₃₃F₆N₂O₇, 1H), 6.87 (d, J = 5.2 Hz, 155.38, 1530, 575.2186; 1H), 4.80 (pd, J = 6.3, 148.75, 1451, found, 1.9 Hz, 1H), 140.55, 1253 575.2191 4.59 (dt, J = 10.8, 7.6 Hz, 130.34, 1H), 3.94 (s, 3H), 128.55, 3.80 (dt, J = 9.3, 6.1 Hz, 125.80, 1H), 3.69 (dt, J = 9.3, 109.50, 84.14, 6.2 Hz, 1H), 83.94, 72.86, 3.58 (dt, J = 9.4, 6.4 Hz, 71.82, 66.89, 1H), 3.42-3.34 (m, 56.09, 51.23, 3H), 2.45-2.32 (m, 33.22, 1H), 2.29-2.05 (m, 30.77 (qd, J = 28.8, 5H), 1.87-1.77 (m, 1.3 Hz), 4H), 1.70-1.61 (m, 27.52, 2H), 1.47-1.33 (m, 22.96 (dd, J = 19.1, 4H), 0.94 (dd, J = 16.2, 3.0 Hz), 7.3 Hz, 1H) 18.11, 17.90; ¹⁹F NMR (CDCl₃) δ −66.37 (dt, J = 25.5, 11.2 Hz) F86 Colorless — 2954, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 1751, (m/z) 8.32 (d, J = 8.1 Hz, (CDCl₃) δ 1678, [M + H]⁺ 1H), 8.28 (d, J = 5.3 Hz, 172.62, 1508 calcd for 1H), 7.06 (d, J = 8.5 Hz, 170.31, C₃₀H₄₁N₂O₉, 2H), 6.97 (d, 162.97, 573.2807; J = 8.6 Hz, 2H), 160.28, found, 6.95 (d, J = 5.4 Hz, 1H), 157.69, 573.2792 5.74 (s, 2H), 145.73, 4.99 (dq, J = 9.6, 6.4 Hz, 144.03, 1H), 4.63 (dt, J = 10.7, 142.38, 7.6 Hz, 1H), 130.51, 4.36 (dd, J = 9.6, 7.3 Hz, 129.77, 1H), 3.91 (s, 3H), 116.32, 3.53 (ddd, J = 7.1, 109.61, 89.55, 5.2, 1.7 Hz, 1H), 83.18, 83.12, 3.24 (dd, J = 8.8, 6.6 Hz, 76.42, 72.73, 1H), 3.08 (dd, J = 8.8, 56.19, 51.65, 6.2 Hz, 1H), 33.46, 28.72, 2.41 (dt, J = 13.8, 6.6 Hz, 27.96, 20.89, 1H), 2.29 (s, 3H), 20.50, 19.40, 2.24-2.13 (m, 1H), 19.26, 18.35, 2.07 (s, 3H), 18.12 1.86-1.65 (m, 3H), 1.43-1.35 (m, 1H), 1.34 (d, J = 6.5 Hz, 3H), 1.03 (dd, J = 16.1, 7.4 Hz, 1H), 0.78 (dd, J = 19.4, 6.7 Hz, 6H) F87 Colorless — 2948, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 1751, (m/z) 8.31 (d, J = 8.1 Hz, (CDCl₃) δ 1679, [M + H]⁺ 1H), 8.28 (d, J = 5.3 Hz, 172.55, 1505, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.31, 1335 C₂₇H₃₇F₆N₂O₉, 1H), 5.74 (s, 163.00 647.2398; 2H), 4.83-4.74 (m, 160.28, found, 1H), 4.61 (dt, J = 10.8, 145.74, 647.2414 7.5 Hz, 1H), 144.03, 3.91 (s, 3H), 3.80 (dt, 142.34, J = 9.3, 6.2 Hz, 1H), 109.62, 89.53, 3.68 (dt, J = 9.2, 6.1 Hz, 84.21, 83.99, 1H), 3.58 (dt, J = 9.3, 72.59, 71.80, 6.3 Hz, 1H), 66.87, 56.19, 3.42-3.33 (m, 3H), 51.57, 33.29, 2.42-2.34 (m, 1H), 30.78 (qd, J = 28.9, 2.26-2.05 (m, 6H), 2.1 Hz), 2.07 (s, 3H), 27.60, 1.88-1.78 (m, 4H), 23.25-22.60 (m), 1.71-1.60 (m, 1H), 1.38 (d, J = 6.3 Hz, 20.88, 18.18, 3H), 17.89; 1.36-1.22 (m, 1H), ¹⁹F NMR 0.99-0.88 (m, 1H) CDCl₃) δ −66.38 (dt, J = 26.8, 11.1 Hz) F88 Colorless — 2956, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2871, (m/z) 8.32 (d, J = 7.9 Hz, (CDCl₃) δ 1737, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 175.85, 1678, calcd for 1H), 6.95 (d, J = 5.4 Hz, 175.51, 1503, C₃₁H₄₃N₂O₁₁, 1H), 5.74 (s, 172.43, 1157 619.2861; 2H), 5.27 (dd, J = 9.8, 170.31, found, 8.1 Hz, 1H), 162.99, 619.2855 5.12-4.95 (m, 2H), 160.28, 4.67 (dt, J = 10.8, 7.6 Hz, 145.72, 1H), 3.91 (s, 3H), 144.07, 2.68 (dtt, J = 10.3, 142.22, 8.6, 7.0 Hz, 2H), 109.65, 89.53, 2.41 (dt, J = 13.8, 7.1 Hz, 74.77, 73.79, 1H), 2.20-2.09 (m, 71.13, 56.20, 1H), 2.07 (s, 3H), 51.51, 43.89, 1.96-1.79 (m, 5H), 43.79, 33.18, 1.79-1.64 (m, 9H), 30.08, 30.01, 1.61-1.49 (m, 4H), 29.93, 29.80, 1.43-1.32 (m, 1H), 29.22, 25.77, 1.29 (d, J = 6.4 Hz, 25.70, 20.88, 3H), 1.18 (ddt, J = 16.2, 18.18, 17.24 7.9, 2.2 Hz, 1H) F89 Yellow Oil — 3376, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 8.52 (d, J = 8.2 Hz, (CDCl₃) δ 2872, [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 172.54, 1772, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.91, 1744, C₂₇H₄₃N₂O₈, 1H), 162.38, 1679, 523.3014; 4.77 (ddq, J = 9.0, 6.2, 3.6 Hz, 159.42, 1508, found, 1H), 146.69, 1197 523.3055 4.67-4.50 (m, 1H), 3.90 (s, 3H), 141.42, 3.80 (dt, J = 9.0, 6.5 Hz, 137.47, 1H), 3.59 (dt, J = 8.9, 109.78, 84.25, 6.7 Hz, 1H), 83.82, 75.96, 3.42-3.21 (m, 3H), 73.87, 73.03, 3.12 (dd, J = 8.8, 6.3 Hz, 56.28, 51.35, 1H), 2.40 (s, 3H), 33.64, 30.06, 2.37-2.29 (m, 1H), 28.86, 28.39, 2.21-2.01 (m, 1H), 27.78, 22.56, 1.82 (dt, J = 13.1, 6.6 Hz, 20.75, 19.53, 2H), 19.48, 18.24, 1.69-1.55 (m, 3H), 17.88, 14.05 1.43-1.19 (m, 8H), 1.00-0.78 (m, 10H) F90 Yellow — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2946, (m/z) 8.49 (d, J = 8.2 Hz, (CDCl₃) δ 2881, [M + H]⁺ 1H), 8.33 (d, J = 5.5 Hz, 172.43, 1772, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.92, 1744, C₂₆H₃₅F₆N₂O₈, 1H), 4.78 (dq, 162.43, 1508, 617.2292; J = 8.4, 6.1 Hz, 1H), 159.45, 1147 found, 4.59 (dt, J = 10.8, 7.7 Hz, 146.70, 617.2297 1H), 3.91 (s, 3H), 141.35, 3.80 (dt, J = 9.3, 6.1 Hz, 137.51, 1H), 3.68 (dt, J = 9.3, 128.55, 6.2 Hz, 1H), 109.83, 84.20, 3.57 (dt, J = 9.3, 6.3 Hz, 83.98, 72.60, 1H), 3.43-3.19 (m, 71.79, 66.88, 3H), 2.40 (s, 3H), 56.30, 51.29, 2.40-2.27 (m, 1H), 33.51, 2.23-1.97 (m, 5H), 30.78 (qd, J = 29.3, 1.88-1.67 (m, 4H), 28.8, 1.4 Hz), 1.67-1.49 (m, 2H), 27.61, 1.37 (d, J = 6.3 Hz, 22.94 (dt, J = 19.7, 3H), 1.34-1.15 (m, 2.9 Hz), 1H), 0.99-0.86 (m, 20.75, 18.13, 1H) 17.87; ¹⁹F NMR (CDCl₃) δ- 66.38 (dt, J = 25.0, 11.1 Hz) F91 Colorless — 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2953, (m/z) 8.49 (d, J = 8.2 Hz, (CDCl₃) δ 2871, [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 175.83 1735, calcd for 1H), 7.01 (d, J = 5.5 Hz, 175.51, 1677, C₃₀H₄₁N₂O₁₀, 1H), 5.25 (dd, 172.31, 1507, 589.2756; J = 9.8, 8.1 Hz, 1H), 168.91, 1157 found, 5.11-4.92 (m, 2H), 162.42, 589.2769 4.66 (dt, J = 10.7, 7.7 Hz, 159.45, 1H), 3.91 (s, 3H), 146.69, 2.82-2.57 (m, 2H), 141.26, 2.42-2.34 (m, 1H), 137.52, 2.40 (s, 3H), 109.85, 74.74, 2.19-2.06 (m, 1H), 73.77, 71.15, 1.93-1.49 (m, 18H), 56.30, 51.21, 1.42-1.31 (m, 1H), 43.87, 43.78, 1.27 (dd, J = 12.1, 6.8 Hz, 30.08, 30.00, 3H), 1.17 (ddt, J = 16.1, 29.94, 29.79, 7.7, 2.3 Hz, 1H) 29.25, 25.77, 25.75, 25.69, 20.75, 18.14, 17.22 F92 Light — 3376, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Yellow 2954, (m/z) 8.53 (d, J = 8.5 Hz, (CDCl₃) δ Semi-Solid 2872, [M + H]⁺ 1H), 8.34 (d, J = 5.4 Hz, 172.50, 1770, calcd for 1H), 168.92, 1744, C₂₉H₃₉N₂O₈, 7.09-7.02 (m, 2H), 162.39, 1506, 543.2701; 7.03-6.94 (m, 3H), 4.99 (dq, J = 9.6, 159.43, 1195 found, 6.4 Hz, 1H), 157.67, 543.2698 4.62 (dt, J = 10.7, 7.7 Hz, 146.70, 1H), 4.34 (dd, J = 9.7, 141.39, 7.3 Hz, 1H), 137.50, 3.91 (s, 3H), 3.52 (ddd, J = 7.1, 130.50, 5.2, 1.7 Hz, 129.76, 1H), 3.23 (dd, J = 8.8, 116.33, 6.6 Hz, 1H), 109.80, 83.18, 3.12-3.00 (m, 1H), 83.10, 76.43, 2.40 (s, 3H), 72.73, 56.29, 2.40-2.30 (m, 1H), 2.29 (s, 3H), 51.36, 33.66, 2.24-2.09 (m, 1H), 28.71, 27.97, 1.72 (ddt, J = 13.2, 20.75, 20.50, 9.5, 6.7 Hz, 3H), 19.39, 19.25, 1.62-1.53 (m, 1H), 18.31, 18.09 1.37-1.28 (m, 3H), 1.07-0.96 (m, 1H), 0.85-0.71 (m, 6H) F93 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 7.37-7.25 (m, 10H), (CDCl₃) δ [M + Na]⁺ 5.89 (dd, J = 18.1, 170.26, calcd for 10.3 Hz, 1H), 5.60 (t, 152.74, C₃₃H₄₃NNaO₈, J = 10.2 Hz, 1H), 138.49, 604.2881; 5.02 (d, J = 10.9 Hz, 138.31, found, 1H), 4.95-4.81 (m, 135.57, 604.2874 1H), 4.66-4.48 (m, 128.54, 3H), 4.43 (d, J = 11.6 Hz, 128.32, 1H), 4.08 (t, J = 9.2 Hz, 128.30, 1H), 3.41 (t, J = 9.0 Hz, 128.23, 1H), 127.69, 3.14 (q, J = 12.0 Hz, 1H), 127.56, 2.37 (dd, J = 12.3, 127.44, 83.80, 7.4 Hz, 1H), 1.49 (s, 82.89, 77.68, 18H), 1.33 (d, J = 6.3 Hz, 75.28, 74.28, 3H) 70.89, 56.96, 33.02, 27.97, 19.17 F94 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.10-12.02 (m, (CDCl₃) δ [M + H]⁺ 1H), 8.47 (d, J = 8.1 Hz, 171.97, calcd for 1H), 7.98 (dd, J = 5.2, 168.69, C₂₇H₃₇N₂O₇, 0.9 Hz, 1H), 157.62 501.2595; 7.32-7.24 (m, 2H), 155.35, found, 6.93 (dddd, J = 12.2, 9.6, 148.73, 501.2603 8.3, 4.1 Hz, 3H), 140.54, 6.86 (d, J = 5.2 Hz, 1H), 130.35, 4.91 (tq, J = 9.0, 6.4 Hz, 129.50, 1H), 4.63 (dtd, J = 11.4, 121.29, 7.7, 3.9 Hz, 116.63, 1H), 4.40 (dt, J = 18.8, 109.49, 83.40, 5.4 Hz, 1H), 83.03, 73.98, 3.93 (s, 3H), 73.04, 56.07, 3.86-3.71 (m, 1H), 51.24 33.22, 3.63 (dt, J = 9.0, 6.7 Hz, 29.95, 28.24, 2H), 2.35 (dq, J = 14.9, 22.44, 18.21, 7.4 Hz, 1H) 17.93, 13.96, 2.30-2.10 (m, 1H), 9.42, 9.21 1.89-1.75 (m, 1H), 1.67-1.55 (m, 1H), 1.55-1.42 (m, 5H), 1.40-1.28 (m, 1H), 1.28-1.17 (m, 3H), 1.05 (dd, J = 16.1, 7.8 Hz, 1H), 0.87 (t, J = 7.5 Hz, 1H), 0.83-0.77 (m, 2H), 0.69 (t, J = 7.4 Hz, 1H) F95 Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR White Foam (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.57, calcd for 1H), 170.27, C₂₈H₃₇N₂O₉, 545.2494; 7.32-7.22 (m, 2H), 163.00, found, 7.02-6.86 (m, 4H), 5.74 (s, 2H), 160.27, 545.2506 4.91 (dq, J = 9.7, 6.4 Hz, 157.68, 1H), 4.65 (dt, J = 10.7, 145.74, 7.6 Hz, 1H), 143.99, 4.37 (t, J = 5.5 Hz, 142.35, 1H), 3.90 (s, 3H), 129.48, 3.73 (dt, J = 8.9, 6.5 Hz, 121.25, 1H), 116.69, 3.68-3.52 (m, 2H), 2.37 (dt, J = 13.6, 109.64, 89.51, 7.0 Hz, 1H), 83.41, 83.19, 2.25-2.09 (m, 1H), 75.57, 72.77, 2.07 (s, 3H), 56.19, 51.58, 1.85-1.76 (m, 1H), 33.29, 28.32, 1.64 (dq, J = 15.4, 7.5 Hz, 23.43, 20.88, 1H), 1.56-1.41 (m, 18.27, 17.92, 5H), 1.37-1.26 (m, 10.60 1H), 1.05 (dd, J = 16.1, 7.8 Hz, 1H), 0.83 (t, J = 7.4 Hz, 3H) F96 Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR White Foam (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (dd, J = 5.4, 172.57, calcd for 0.8 Hz, 1H), 170.27, C₃₀H₄₀N₂NaO₉, 7.31-7.22 (m, 2H), 162.99, 595.2626; 6.98-6.84 (m, 4H), 160.26, found, 5.74 (s, 2H), 157.67, 595.2659 4.96-4.82 (m, 1H), 4.65 (dtd, J = 11.4, 145.73, 7.6, 4.0 Hz, 143.99, 1H), 4.39 (dt, J = 18.7, 142.35, 5.4 Hz, 1H), 129.47, 3.90 (s, 3H), 121.23, 3.85-3.70 (m, 1H), 116.64, 3.62 (ddd, J = 9.0, 7.0, 5.1 Hz, 109.63, 89.51, 2H), 2.36 (dq, J = 14.3, 83.45, 83.12, 7.3 Hz, 1H), 73.95, 72.76, 2.28-2.10 (m, 1H), 56.19, 51.58, 2.07 (s, 3H), 33.29, 29.95, 1.89-1.75 (m, 1H), 28.24, 25.30, 1.64 (ddt, J = 15.0, 11.7, 22.43, 20.87, 7.4 Hz, 1H), 18.28, 17.92, 1.54-1.42 (m, 5H), 13.96, 9.41, 1.36-1.27 (m, 1H), 1.26 (s, 9.20 3H), 1.10-0.99 (m, 1H), 0.86 (t, J = 7.5 Hz, 1H), 0.83-0.76 (m, 2H), 0.69 (t, J = 7.4 Hz, 1H) F97 Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR White Foam (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.24, calcd for 1H), 172.56, C₃₀H₄₁N₂O₉, 7.32-7.20 (m, 2H), 162.97, 573.2807; 6.99-6.88 (m, 4H), 160.24, found, 5.81-5.72 (m, 2H), 4.91 (dq, J = 9.6, 157.68, 573.2795 6.4 Hz, 1H), 145.60, 4.65 (dt, J = 10.7, 7.6 Hz, 144.20, 1H), 4.37 (t, J = 5.4 Hz, 142.01, 1H), 3.88 (s, 3H), 129.48, 3.73 (dt, J = 8.9, 6.5 Hz, 121.24, 1H), 116.68, 3.67-3.53 (m, 2H), 2.55 (p, J = 7.0 Hz, 109.57, 89.87, 1H), 2.37 (dt, 83.41, 83.19, J = 13.6, 7.0 Hz, 1H), 75.57, 72.75, 2.16 (dddd, J = 15.7, 56.14 51.57, 10.1, 6.4, 4.0 Hz, 33.85, 33.30, 1H), 1.88-1.78 (m, 28.31, 23.43, 1H), 1.63 (tt, J = 16.0, 18.67, 18.27, 8.2 Hz, 1H) 17.92, 10.59 1.55-1.41 (m, 5H), 1.36-1.23 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 1.05 (dd, J = 16.1, 7.8 Hz, 1H), 0.83 (t, J = 7.4 Hz, 3H) F98 Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR White Foam (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.26 (dd, J = 5.4, 176.24, calcd for 0.9 Hz, 1H), 172.57, C₃₂H₄₅N₂O₉, 7.31-7.20 (m, 2H), 162.97, 601.3120; 6.99-6.84 (m, 4H), 160.24, found, 5.83-5.73 (m, 2H), 157.67, 601.3131 4.96-4.80 (m, 1H), 145.60, 4.64 (dtd, J = 11.3, 7.6, 144.20, 3.9 Hz, 1H), 4.39 (dt, 142.02, J = 18.7, 5.5 Hz, 1H), 129.47, 3.88 (s, 3H), 121.22, 3.84-3.72 (m, 1H), 116.63, 3.62 (ddd, J = 9.0, 6.9, 5.4 Hz, 109.58, 89.87, 2H), 83.46, 83.11, 2.62-2.47 (m, 1H), 2.36 (dq, J = 14.3, 73.95, 72.75, 7.3 Hz, 1H), 56.14, 51.57, 2.26-2.08 (m, 1H), 33.85, 33.30, 1.88-1.74 (m, 1H), 29.95, 28.33, 1.64 (ddt, J = 14.8, 28.24, 25.32, 11.5, 7.3 Hz, 1H), 25.30, 22.43, 1.53-1.40 (m, 5H), 18.68, 18.28, 1.36-1.26 (m, 1H), 17.92, 13.96, 1.23 (td, J = 8.2, 6.7, 9.41, 9.20 4.6 Hz, 3H), 1.14 (d, J = 7.0 Hz, 6H), 1.10-1.00 (m, 1H), 0.86 (t, J = 7.5 Hz, 1H), 0.83-0.76 (m, 2H), 0.69 (t, J = 7.4 Hz, 1H) F99 Yellow — 3376, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2955, (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ 2872, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.28, 1738, calcd for 1H), 6.94 (d, J = 5.4 Hz, 175.84, 1679, C₃₃H₄₇N₂O₁₁, 1H), 175.51, 1504, 647.3174; 5.81-5.72 (m, 2H), 172.42, 1157 found 5.27 (dd, J = 9.8, 8.1 Hz, 162.97, 647.3187 1H), 5.11-4.95 (m, 160.26, 2H), 4.66 (dt, J = 10.8, 145.58, 7.6 Hz, 1H), 144.27, 3.89 (s, 3H), 141.89, 2.74-2.62 (m, 2H), 2.55 (p, 109.60, 89.87, J = 7.0 Hz, 1H), 74.78, 73.79, 2.40 (dt, J = 13.8, 7.1 Hz, 71.11, 56.14, 1H), 2.22-2.04 (m, 51.51, 43.89, 1H), 1.96-1.79 (m, 43.79, 33.86, 6H), 1.78-1.67 (m, 33.17, 30.08, 8H), 1.60-1.50 (m, 30.00, 29.93, 5H), 1.45-1.34 (m, 29.79, 29.21, 1H), 1.29 (d, J = 6.3 Hz, 25.77, 25.75, 3H), 1.14 (d, J = 7.0 Hz, 25.70, 18.68, 6H) 18.18, 17.24 F100 Colorless — 3382, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2943, (m/z) 8.36 (d, J = 8.0 Hz, (CDCl₃) δ 2880, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.28, 1746, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.55, 1678, C₂₉H₄₁F₆N₂O₉, 1H), 163.00, 1504, 675.2711; 5.84-5.72 (m, 2H), 160.28, 1253, found, 4.78 (pd, J = 6.4, 2.2 Hz, 145.63, 1103 675.2713 1H), 4.60 (dt, J = 10.7, 144.24, 10.7, 7.5 Hz, 1H), 142.01, 3.89 (s, 3H), 3.80 (dt, 127.21 (q, J = 276.0 Hz), J = 9.3, 6.1 Hz, 1H), 109.61, 89.89, 3.68 (dt, J = 9.1, 6.2 Hz, 84.22, 84.01, 1H), 3.58 (dt, J = 9.1, 72.59, 71.81, 6.3 Hz, 1H), 66.87, 56.16, 3.42-3.31 (m, 3H), 51.58, 33.87, 2.55 (p, J = 7.0 Hz, 1H), 33.30, 2.42-2.32 (m, 1H), 30.79 (qd, J = 28.7, 2.26-2.06 (m, 5H), 2.1 Hz), 1.86-1.79 (m, 4H), 27.60, 1.72-1.58 (m, 2H), 22.97 (dd, J = 19.7, 1.39 (d, J = 6.3 Hz, 2.9 Hz), 3H), 1.35-1.28 (m, 18.68, 18.20, 1H), 1.14 (d, J = 7.0 Hz, 17.90; 6H), ¹⁹F NMR 1.00-0.88 (m, 1H) (CDCl₃) δ- 66.40 (dt, J = 25.3, 11.2 Hz) F101 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2954, (m/z) 8.38 (d, J = 8.0 Hz, (CDCl₃) δ 2874, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.26, 1745, calcd for 1H), 7.06 (d, J = 8.4 Hz, 172.61, 1677, C₃₂H₄₅N₂O₉, 2H), 6.98 (d, 162.95, 1506, 601.3120; J = 8.6 Hz, 2H), 160.25, 1205 found, 6.94 (d, J = 5.4 Hz, 1H), 157.69, 601.3105 5.87-5.69 (m, 2H), 145.60, 4.99 (dq, J = 9.6, 6.4 Hz, 144.22, 1H), 4.63 (dt, J = 10.8, 142.03, 7.5 Hz, 1H), 130.49, 4.36 (dd, J = 9.6, 7.3 Hz, 129.76, 1H), 3.89 (s, 3H), 116.32, 3.53 (ddd, J = 7.2, 116.29, 5.2, 1.7 Hz, 1H), 109.57, 89.88, 3.24 (dd, J = 8.8, 6.7 Hz, 83.18, 83.11, 1H), 3.08 (dd, J = 8.8, 76.41, 72.70, 6.2 Hz, 1H), 56.14, 51.64, 2.55 (p, J = 7.0 Hz, 1H), 33.85, 33.44, 2.48-2.35 (m, 1H), 28.71, 27.94, 2.29 (s, 3H), 20.50, 19.40, 2.19 (dddd, J = 15.7, 10.3, 19.25, 18.68, 8.3, 5.3 Hz, 1H), 18.36, 18.11 1.77-1.61 (m, 3H), 1.42-1.27 (m, 4H), 1.14 (d, J = 7.0 Hz, 6H), 1.07-0.96 (m, 1H), 0.78 (dd, J = 19.4, 6.7 Hz, 6H) F102 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.52 (d, J = 6.7 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.45, calcd for 1H), 7.27 (t, J = 7.9 Hz, 168.89, C₂₇H₃₄N₂NaO₉, 2H), 6.99 (d, 162.42, 537.2207; J = 5.5 Hz, 1H), 159.44, found, 6.95 (t, J = 8.7 Hz, 3H), 157.68, 537.2210 4.96-4.84 (m, 1H), 146.70, 4.64 (dt, J = 10.5, 7.9 Hz, 141.35, 1H), 4.36 (t, J = 5.5 Hz, 137.49, 1H), 3.89 (s, 129.48, 3H), 3.73 (dt, J = 8.7, 121.25, 6.5 Hz, 1H), 116.68, 3.67-3.51 (m, 2H), 109.83, 83.40, 2.47-2.26 (m, 4H), 83.20, 75.57, 2.23-2.07 (m, 1H), 72.78, 56.29, 1.86-1.74 (m, 1H), 51.30, 33.50, 1.62 (dq, J = 16.4, 9.0, 8.4 Hz, 28.34, 23.43, 1H), 20.74, 18.24, 1.55-1.40 (m, 5H), 17.90, 10.59 1.33-1.23 (m, 1H), 1.04 (dd, J = 16.0, 7.7 Hz, 1H), 0.83 (t, J = 7.4 Hz, 3H) F103 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.52 (d, J = 6.6 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.45, calcd for 1H), 168.89, C₂₉H₃₈N₂NaO₉, 7.32-7.23 (m, 1H), 7.00 (d, J = 5.5 Hz, 162.42, 560.2966; 1H), 159.44, found, 6.97-6.85 (m, 3H), 157.67, 560.2954 4.88 (dtd, J = 9.5, 6.4, 3.2 Hz, 146.69, 1H), 4.63 (ddq, J = 11.6, 141.36, 8.0, 4.1 Hz, 137.50, 1H), 4.39 (dt, J = 18.8, 129.47, 18.8, 5.5 Hz, 1H), 121.23, 3.90 (s, 3H), 116.64, 3.77 (ddt, J = 13.0, 8.9, 109.82, 83.44, 6.7 Hz, 1H), 83.13, 73.95, 3.66-3.57 (m, 2H), 2.40 (s, 72.77, 56.28, 4H), 2.27-2.07 (m, 51.29, 33.51, 1H), 1.86-1.71 (m, 29.95, 28.24, 1H), 1.69-1.56 (m, 25.30, 22.43, 1H), 1.46 (dd, J = 13.0, 20.74, 17.89, 13.0, 5.7 Hz, 5H), 13.95, 9.19 1.31-1.17 (m, 5H), 1.10-0.94 (m, 1H), 0.86 (t, J = 7.5 Hz, 1H), 0.83-0.76 (m, 2H), 0.68 (t, J = 7.4 Hz, 1H) F104 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.04 (d, J = 0.5 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.46 (d, J = 8.1 Hz, 171.88, calcd for 1H), 7.98 (d, J = 5.2 Hz, 168.72, C₂₆H₃₀F₃N₂O₇, 1H), 157.08, 540.2032; 7.31-7.24 (m, 2H), 155.37, found 7.03-6.94 (m, 1H), 148.74, 540.2038 6.91 (dd, J = 8.7, 1.0 Hz, 140.56, 2H), 6.87 (d, J = 5.2 Hz, 6.39 (q, J = 6.4 Hz), 1H), 6.33 (ddq, J = 15.7, 130.29, 4.2, 2.1 Hz, 129.66, 1H), 5.89-5.74 (m, 125.64 (q, J = 269.1 Hz), 1H), 4.98 (dq, J = 9.6, 121.67, 6.4 Hz, 1H), 118.43 (q, J = 34.1 Hz), 4.64 (dt, J = 10.7, 7.6 Hz, 116.55, 1H), 4.51-4.39 (m, 109.53, 83.80, 2H), 4.35-4.24 (m, 82.70, 72.39, 1H), 3.94 (s, 3H), 71.00, 56.08, 3.74 (dd, J = 9.6, 7.2 Hz, 51.20, 33.12, 1H), 2.37 (dt, J = 13.6, 28.16, 18.17, 7.1 Hz, 1H), 17.98 2.20 (tdd, J = 13.3, 6.3, 3.9 Hz, 1H), 1.90-1.75 (m, 1H), 1.73-1.62 (m, 1H), 1.47 (d, J = 6.4 Hz, 3H), 1.43-1.31 (m, 1H), 1.09 (dd, J = 16.2, 7.8 Hz, 1H) F105 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.04 (s, 1H), (CDCl₃) δ [M + Na]⁺ 8.46 (d, J = 8.1 Hz, 1H), 171.93, calcd for 7.98 (d, J = 5.2 Hz, 168.70, C₂₆H₃₁F₃N₂NaO₇, 1H), 7.32-7.28 (m, 157.30, 563.1976; 1H), 6.97 (t, J = 7.4 Hz, 155.37, found, 1H), 148.74, 563.2009 6.93-6.89 (m, 2H), 6.87 (d, J = 5.2 Hz, 140.55, 1H), 4.93 (dq, 130.31, J = 9.6, 6.4 Hz, 1H), 129.61, 4.64 (dt, J = 10.7, 7.6 Hz, 127.14 (q, J = 276.0 Hz), 1H), 4.38 (t, J = 5.5 Hz, 121.45, 1H), 3.94 (s, 116.31, 3H), 3.80 (dt, J = 9.1, 109.51, 83.63, 6.1 Hz, 1H), 3.71 (dt, 82.48, 72.70, J = 9.2, 5.9 Hz, 1H), 71.85, 56.08, 3.65 (dd, J = 9.6, 7.2 Hz, 51.22, 33.17, 1H), 2.36 (dt, J = 13.7, 30.54 (q, J = 28.9 Hz), 7.0 Hz, 1H), 28.25, 2.27-2.13 (m, 1H), 22.93 (q, J = 2.7 Hz), 2.03 (ddddd, J = 29.6, 18.16, 14.8, 11.3, 6.9, 17.93 3.3 Hz, 2H), 1.90-1.76 (m, 1H), 1.76-1.59 (m, 4H), 1.46 (d, J = 6.4 Hz, 3H), 1.42-1.29 (m, 1H), 1.07 (dd, J = 16.1, 7.8 Hz, 1H) F106 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.48, calcd for 1H), 170.28, C₂₉H₃₄F₃N₂O₉, 7.31-7.23 (m, 2H), 163.02, 611.2211 7.01-6.87 (m, 4H), 6.32 (ddq, J = 15.7, 160.28, found 4.1, 2.1 Hz, 157.14, 611.2213 1H), 5.88-5.75 (m, 145.74, 1H), 5.74 (s, 2H), 144.01, 4.96 (dq, J = 9.7, 6.4 Hz, 142.27, 1H), 4.66 (dt, J = 10.7, 136.45 (q, J = 6.4 Hz), 7.6 Hz, 1H), 129.62, 4.51-4.37 (m, 2H), 122.98 (q, J = 269.2 Hz), 4.33-4.24 (m, 1H), 121.60, 3.91 (s, 3H), 118.36 (q, J = 34.1 Hz), 3.73 (dd, J = 9.6, 7.2 Hz, 116.56, 1H), 2.37 (dt, J = 13.6, 109.67, 89.48, 13.6, 7.0 Hz, 1H), 83.87, 82.77, 2.28-2.11 (m, 1H), 72.12, 70.99, 2.07 (s, 3H), 1.80 (s, 56.19, 51.55, 1H), 1.64 (dq, J = 15.5, 33.17, 28.23, 7.7 Hz, 1H), 20.86, 18.24, 1.46 (d, J = 6.4 Hz, 17.96 3H), 1.32 (q, J = 11.1 HZ, 1H), 1.08 (dd, J = 16.2, 7.7 Hz, 1H) F107 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.54, calcd for 1H), 170.28, C₂₉H₃₆F₃N₂O₉, 7.34-7.20 (m, 2H), 163.01, 613.2367; 7.01-6.88 (m, 4H), 5.74 (s, 2H), 160.28, found, 4.91 (dq, J = 9.6, 6.4 Hz, 157.36, 613.2398 1H), 4.65 (dt, J = 10.7, 145.73, 7.6 Hz, 1H), 144.01, 4.37 (t, J = 5.5 Hz, 142.30, 1H), 3.91 (s, 3H), 129.59, 3.79 (dt, J = 9.1, 6.1 Hz, 127.15 (q, J = 276.0 Hz), 1H), 3.71 (dt, J = 9.2, 121.38, 5.9 Hz, 1H), 116.32, 3.64 (dd, J = 9.6, 7.3 Hz, 109.65, 89.51, 1H), 2.37 (dt, J = 13.7, 83.68, 82.56, 7.0 Hz, 1H), 72.42, 71.83, 2.26-2.12 (m, 1H), 56.19, 51.56, 2.10-1.89 (m, 5H), 33.24, 1.85-1.61 (m, 4H), 30.69 (q, J = 29.0 Hz), 1.44 (d, J = 6.4 Hz, 28.33, 3H), 1.31 (q, J = 11.1 Hz, 22.93 (q, J = 2.9 Hz), 1H), 1.07 (dd, J = 16.1, 20.87, 18.24, 7.8 Hz, 1H) 17.92 F108 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.25, calcd for 1H), 172.53, C₃₁H₄₀F₃N₂O₉, 7.32-7.21 (m, 2H), 162.98, 641.2680; 7.00-6.87 (m, 4H), 5.77 (d, J = 1.5 Hz, 160.26, found, 2H), 4.91 (dq, 157.36, 641.2686 J = 9.6, 6.4 Hz, 1H), 145.60, 4.65 (dt, J = 10.7, 7.6 Hz, 144.23, 1H), 4.37 (t, J = 5.5 Hz, 141.97, 1H), 3.89 (s, 129.58, 3H), 3.75 (ddt, J = 33.0, 127.15 (q, J = 276.1 Hz), 9.2, 6.0 Hz, 121.38, 2H), 3.64 (dd, J = 9.6, 116.32, 7.3 Hz, 1H), 109.58, 89.87, 2.55 (hept, J = 7.0 Hz, 83.69, 82.56, 1H), 2.36 (dt, J = 13.6, 72.40, 71.83, 7.0 Hz, 1H), 56.14, 51.56, 2.24-2.10 (m, 1H), 33.85, 33.25, 2.02 (ddddt, J = 29.4, 30.69 (q, J = 29.0 Hz), 15.3, 11.0, 7.5, 3.4 Hz, 28.32, 2H), 22.93 (q, J = 2.9 Hz), 1.85-1.62 (m, 4H), 1.44 (d, J = 6.4 Hz, 18.67, 3H), 18.24, 17.92 1.40-1.24 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 1.07 (dd, J = 16.1, 7.8 Hz, 1H) F109 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.52 (d, J = 7.6 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.42, calcd for 1H), 168.89, C₂₈H₃₄F₃N₂O₈, 7.32-7.22 (m, 2H), 7.00 (d, J = 5.5 Hz, 162.44, 583.2262; 1H), 159.45, found, 6.98-6.93 (m, 1H), 157.36, 583.2270 6.91 (dd, J = 8.7, 1.0 Hz, 146.70, 2H), 4.91 (dq, J = 9.6, 141.32, 6.4 Hz, 1H), 137.51, 4.64 (dt, J = 10.7, 7.6 Hz, 129.59, 1H), 4.41-4.33 (m, 127.15 (q, J = 276.0 Hz), 1H), 3.90 (s, 3H), 121.39, 3.74 (ddt, J = 33.5, 116.32, 9.2, 6.0 Hz, 2H), 109.85, 83.67, 3.62 (dd, J = 9.6, 7.2 Hz, 82.56, 72.43, 1H), 2.40 (s, 3H), 71.82, 56.29, 2.35 (dt, J = 13.5, 7.0 Hz, 51.28, 33.46, 1H), 2.16 (dddd, 30.69 (q, J = 28.9 Hz), J = 15.8, 10.1, 6.2, 28.36, 3.8 Hz, 1H), 22.93 (q, J = 3.0 Hz), 2.10-1.88 (m, 2H), 20.74, 1.82-1.59 (m, 4H), 1.43 (d, 18.20, 17.90 J = 6.4 Hz, 3H), 1.34-1.23 (m, 1H), 1.06 (dd, J = 16.1, 7.7 Hz, 1H) F110 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.50 (d, J = 7.2 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.42, calcd for 1H), 169.42, C₃₀H₃₈F₃N₂O₉, 7.32-7.20 (m, 2H), 162.39, 627.2524; 7.01-6.93 (m, 2H), 6.90 (dd, J = 8.7, 159.45, found, 1.0 Hz, 2H), 157.36, 627.2539 4.90 (dq, J = 9.6, 6.4 Hz, 146.76, 1H), 4.63 (dt, J = 10.7, 141.35, 7.6 Hz, 1H), 137.36, 4.37 (t, J = 5.4 Hz, 129.59, 1H), 3.89 (s, 3H), 127.15 (q, J = 276.0 Hz), 3.85-3.75 (m, 3H), 121.39, 3.74-3.66 (m, 1H), 116.31, 3.62 (dd, J = 9.6, 7.2 Hz, 109.85, 83.67, 1H), 3.41 (s, 3H), 82.56, 72.42, 2.98 (t, J = 6.6 Hz, 71.82, 67.57, 2H), 2.33 (dt, J = 13.7, 58.78, 56.32, 7.0 Hz, 1H), 51.26, 34.62, 2.23-1.88 (m, 3H), 33.45, 1.81-1.54 (m, 4H), 30.68 (q, J = 28.9 Hz), 1.43 (d, J = 6.4 Hz, 28.34, 3H), 1.37-1.20 (m, 22.92 (q, J = 3.0 Hz), 1H), 1.06 (dd, J = 16.1, 18.21, 17.89 7.7 Hz, 1H) F111 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.06 (s, 1H), (CDCl₃) δ [M + H]⁺ 8.47 (d, J = 8.1 Hz, 1H), 171.98, calcd for 7.98 (d, J = 5.2 Hz, 168.70, C₃₁H₃₇N₂O₇, 1H), 7.31-7.17 (m, 157.51, 549.2595; 4H), 7.17-7.11 (m, 155.36, found, 1H), 7.11-7.04 (m, 148.74, 549.2610 2H), 7.00-6.89 (m, 141.91, 3H), 6.86 (d, J = 5.2 Hz, 140.55, 1H), 4.94 (dq, J = 9.6, 130.35, 6.4 Hz, 1H), 129.56, 4.63 (dt, J = 10.7, 7.7 Hz, 128.35, 1H), 4.41 (t, J = 5.5 Hz, 128.27, 1H), 3.93 (s, 3H), 125.71, 3.79 (dt, J = 9.1, 6.3 Hz, 121.33, 1H), 116.57, 3.72-3.62 (m, 2H), 109.51, 83.51, 2.66-2.52 (m, 2H), 2.36 (dt, J = 13.6, 82.81, 73.09, 7.0 Hz, 1H), 72.99, 56.08, 2.26-2.11 (m, 1H), 51.25, 33.20, 1.88-1.75 (m, 3H), 32.32, 31.87, 1.66 (t, J = 6.8 Hz, 28.20, 18.20, 1H), 1.48 (d, J = 6.4 Hz, 18.01 3H), 1.35 (q, J = 11.0 Hz, 1H), 1.06 (dd, J = 16.1, 7.8 Hz, 1H) F112 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Foam (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.26 (d, J = 5.3 Hz, 176.26, calcd for 1H), 172.58, C₃₆H₄₅N₂O₉, 7.30-7.18 (m, 4H), 162.98, 649.3120; 7.18-7.11 (m, 1H), 160.25, found, 7.11-7.04 (m, 2H), 157.57, 649.3133 7.01-6.88 (m, 4H), 145.61, 5.81-5.73 (m, 2H), 4.92 (dq, J = 9.6, 144.21, 6.4 Hz, 1H), 142.02, 4.65 (dt, J = 10.7, 7.6 Hz, 141.94, 1H), 4.40 (t, J = 5.5 Hz, 129.54, 1H), 3.88 (s, 3H), 128.34, 3.79 (dt, J = 9.1, 6.3 Hz, 128.26, 1H), 3.66 (ddd, J = 12.6, 125.69, 9.4, 6.7 Hz, 121.27, 2H), 2.62-2.47 (m, 116.57, 3H), 2.36 (dt, J = 13.6, 109.58, 89.88, 7.0 Hz, 1H), 83.57, 82.89, 2.23-2.10 (m, 1H), 73.08, 72.70, 1.88-1.71 (m, 4H), 56.14, 51.58, 1.63 (dq, J = 15.7, 33.86, 33.28, 7.8 Hz, 1H), 1.47 (d, 32.32, 31.88, J = 6.4 Hz, 3H), 28.28, 18.69, 1.37-1.23 (m, 1H), 18.27, 18.00 1.14 (d, J = 7.0 Hz, 6H), 1.06 (dd, J = 16.1, 7.8 Hz, 1H) F113 White Solid — 3369, HRMS-ESI 1H NMR (CDCl₃) δ ¹³C NMR 2941, (m/z) 12.04 (s, 1H), (CDCl₃) δ 1745, [M + H]⁺ 8.47 (d, J = 8.1 Hz, 1H), 171.92, 1650, calcd for 7.99 (d, J = 5.2 Hz, 168.69, 1529 C₃₀H₃₅N₂O₇, 1H), 7.08-6.94 (m, 157.54, 535.2439; 6H), 6.87 (d, J = 5.1 Hz, 155.43, found, 1H), 6.78 (d, J = 8.5 Hz, 155.37, 535.2432 2H), 5.12 (dq, 148.74, J = 9.6, 6.5 Hz, 1H), 140.55, 4.78-4.52 (m, 2H), 131.00, 4.46 (ddd, J = 7.2, 130.92, 5.3, 1.7 Hz, 1H), 130.32, 3.94 (s, 3H), 2.41 (dt, J = 13.7, 129.89, 7.1 Hz, 1H), 117.08, 2.26 (d, J = 7.0 Hz, 116.46, 7H), 1.91 (q, J = 11.4, 109.50, 82.88, 9.2 Hz, 1H), 82.70, 72.81, 1.76 (dq, J = 15.4, 56.08, 51.24, 7.7 Hz, 1H), 1.43 (d, 33.25, 28.05, J = 6.5 Hz, 3H), 20.52, 20.50, 1.42-1.38 (m, 1H), 18.27, 18.20 1.19-0.99 (m, 1H) F114 White Solid — 3370, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2960, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2938, [M + H]⁺ 8.48 (d, J = 8.2 Hz, 1H), 172.04, 2876, calcd for 7.98 (d, J = 5.2 Hz, 168.65, 1743, C₂₂H₃₅N₂O₇, 1H), 6.87 (d, J = 5.2 Hz, 155.34, 1650, 439.2439; 1H), 4.80 (pd, J = 6.3, 148.71, 1529, found, 2.1 Hz, 1H), 140.52, 1265 439.2461 4.66-4.38 (m, 1H), 130.40, 3.94 (s, 3H), 3.78 (dt, J = 9.0, 109.46, 84.16, 6.5 Hz, 1H), 83.76, 75.50, 3.54 (ddt, J = 30.9, 9.0, 73.30, 70.92, 6.6 Hz, 2H), 56.07, 51.30, 3.43-3.25 (m, 3H), 33.36, 27.90, 2.37 (dddd, J = 13.6, 8.0, 23.53, 23.36, 6.3, 2.0 Hz, 1H), 18.24, 17.91, 2.24-2.06 (m, 1H), 10.78, 10.70 1.75-1.52 (m, 6H), 1.44-1.31 (m, 4H), 0.98-0.81 (m, 7H) F115 White Solid — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2943, (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) δ 1751, [M + H]⁺ 1H), 8.28 (d, J = 5.3 Hz, 172.54, 1678, calcd for 1H), 170.31, 1506, C₃₃H₃₉N₂O₉, 7.10-6.92 (m, 7H), 6.77 (d, J = 8.6 Hz, 162.99, 1202 607.2650; 2H), 5.74 (s, 160.28, found, 2H), 5.10 (dq, J = 9.6, 157.59, 607.2672 6.3 Hz, 1H), 155.49, 4.67 (dt, J = 10.7, 7.6 Hz, 145.73, 1H), 4.58 (dd, J = 9.5, 144.05, 7.3 Hz, 1H), 142.30, 4.49-4.40 (m, 1H), 130.94, 3.91 (s, 3H), 2.41 (dt, J = 13.7, 130.86, 7.1 Hz, 1H), 129.87, 2.26 (s, 3H), 2.25 (s, 117.09, 3H), 2.24-2.19 (m, 116.47, 1H), 2.07 (s, 3H), 109.63, 89.54, 1.96-1.83 (m, 1H), 82.98, 82.77, 1.75 (d, J = 8.0 Hz, 72.54, 56.19, 1H), 1.41 (d, J = 6.4 Hz, 51.59, 33.32, 3H), 28.14, 20.89, 1.39-1.24 (m, 1H), 1.13 (dd, J = 16.0, 20.50, 18.35, 7.6 Hz, 1H) 18.20 F116 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 2960, (m/z) 8.32 (d, J = 8.1 Hz, (CDCl₃) δ 2937, [M + Na]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.66, 2876, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.29, 1745, C₂₅H₃₈N₂NaO₉, 1H), 5.74 (s, 162.97, 1676, 533.2470; 2H), 4.79 (ddq, J = 13.6, 160.26, 1503, found, 6.6, 4.4, 3.2 Hz, 145.75, 1236 533.2488 1H), 4.60 (dt, J = 10.7, 143.97, 7.6 Hz, 1H), 142.41, 3.91 (s, 3H), 3.77 (dt, 109.61, 89.53, J = 8.9, 6.5 Hz, 1H), 84.24, 83.81, 3.58 (dt, J = 9.0, 6.7 Hz, 75.48, 73.01, 1H), 3.50 (dt, J = 9.0, 70.89, 56.19, 6.6 Hz, 1H), 51.63, 33.43, 3.42-3.22 (m, 3H), 27.96, 23.52, 2.38 (dtd, J = 13.7, 6.7, 23.36, 20.88, 1.7 Hz, 1H), 18.30, 17.90, 2.16-2.08 (m, 1H), 2.07 (s, 10.78, 10.70 3H), 1.73-1.50 (m, 6H), 1.39 (d, J = 6.3 Hz, 3H), 1.36-1.26 (m, 1H), 0.97-0.85 (m, 7H) F117 Off-White — — HRMS FAB (m/z) ¹H NMR (CDCl₃) ¹³CNMR Amorphous [M]⁺ δ 12.08 (s, 1H), (CDCl₃) δ Solid calcd for 8.47 (d, J = 8.2 Hz, 1H), 172.0, 168.7, C₂₄H₃₄N₂O₇, 7.98 (d, J = 5.1 Hz, 155.3, 148.7, 462.2378; 1H), 6.87 (d, J = 5.2 Hz, 140.5, 130.4, found, 1H), 109.5, 84.1, 462.2366 4.88-4.78 (m, 1H), 4.59 (dt, J = 10.7, 83.4, 78.7, 7.5 Hz, 1H), 74.0, 73.2, 3.94 (s, 3H), 56.1, 51.3, 3.79-3.60 (m, 2H), 33.3, 28.0, 3.53-3.47 (m, 1H), 18.3, 17.9, 3.47-3.39 (m, 2H), 11.1, 11.0, 3.39-3.24 (m, 2H), 3.1, 3.1, 2.9, 2.42-2.31 (m, 1H), 2.9 2.19-2.06 (m, 1H), 1.76-1.59 (m, 2H), 1.43 (d, J = 6.4 Hz, 3H), 1.41-1.32 (m, 1H), 1.15-1.00 (m, 2H), 0.98-0.89 (m, 1H), 0.60-0.49 (m, 4H), 0.27-0.16 (m, 4H) F118 White Solid 119-121 3694, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR 3369, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2958, [M + H]⁺ 8.47 (d, J = 8.2 Hz, 1H), 172.07, 2873, calcd for 7.99 (d, J = 5.2 Hz, 168.64, 1739, C₂₄H₃₇N₂O₇, 1H), 6.86 (d, J = 5.2 Hz, 155.33, 1650, 465.2595; 1H), 4.80 (dq, J = 9.6, 148.70, 1576, found, 6.4 Hz, 1H), 140.50, 1528 465.2601 4.58 (dt, J = 10.7, 7.7 Hz, 130.39, 1H), 4.07-3.97 (m, 109.45, 83.72, 1H), 3.94 (s, 3H), 81.67, 79.20, 3.78 (dt, J = 8.8, 6.6 Hz, 75.84, 73.46, 1H), 3.55 (dt, J = 8.7, 56.06, 51.31, 6.9 Hz, 1H), 33.53, 33.39, 3.42 (ddd, J = 7.1, 5.1, 1.7 Hz, 31.90, 28.37, 1H), 3.32 (dd, J = 9.5, 23.65, 23.52, 7.4 Hz, 1H), 23.34, 18.47, 2.37 (dtd, J = 13.7, 7.2, 17.85, 10.66 6.5, 1.9 Hz, 1H), 2.09 (dddd, J = 15.5, 10.0, 8.2, 5.0 Hz, 1H), 1.79-1.47 (m, 13H), 1.41 (d, J = 6.4 Hz, 3H), 0.93 (t, J = 7.4 Hz, 3H), 0.90-0.85 (m, 1H) F119 Colorless 99-100 3368, ESIMS ¹H NMR (CDCl₃) δ ¹³CNMR Clear Solid 2957, m/z 479.4 12.09 (s, 1H), (CDCl₃) δ 2871, ([M + H]⁺); 8.47 (d, J = 8.2 Hz, 1H), 172.07, 1744, HRMS-ESI 7.98 (d, J = 5.2 Hz, 168.64, 1650, (m/z) 1H), 6.86 (d, J = 5.2 Hz, 155.33, 1529 [M + H]⁺ 1H), 4.81 (dq, J = 9.5, 148.71, calcd for 6.4 Hz, 1H), 140.50, C₂₅H₃₉N₂O₇, 4.58 (dt, J = 10.8, 7.6 Hz, 130.40, 479.2752; 1H), 4.01 (dtd, J = 7.2, 109.45, 83.71, found, 3.7, 1.2 Hz, 1H), 81.71, 80.94, 479.2766 3.94 (s, 3H), 79.17, 73.52, 3.65 (dd, J = 8.5, 5.9 Hz, 56.06, 51.31, 1H), 3.44 (ddd, J = 7.2, 33.57, 33.38, 5.3, 1.7 Hz, 1H), 31.89, 29.17, 3.32 (ddd, J = 9.5, 28.37, 23.67, 7.2, 3.1 Hz, 2H), 23.38, 19.60, 2.37 (dtd, J = 13.9, 7.1, 19.40, 18.48, 6.6, 1.8 Hz, 1H), 17.93 2.17-2.05 (m, 1H), 1.90-1.77 (m, 1H), 1.77-1.57 (m, 10H), 1.57-1.46 (m, 2H), 1.40 (d, J = 6.4 Hz, 3H), 0.93 (d, J = 6.6 Hz, 3H), 0.90 (d, J = 6.7 Hz, 3H) F120 White Solid 43-48 3368, ESIMS ¹H NMR (CDCl₃) δ ¹³CNMR 2946, m/z 533.3 12.07 (s, 1H), (CDCl₃) δ 2873, ([M + H]⁺); 8.46 (d, J = 8.1 Hz, 1H), 172.03, 1743, HRMS-ESI 7.99 (d, J = 5.2 Hz, 168.66, 1650, (m/z) 1H), 6.87 (d, J = 5.2 Hz, 155.35, 1576, [M + H]⁺ 1H), 4.80 (dq, J = 9.5, 148.73, 1527 calcd for 6.4 Hz, 1H), 140.52, C₂₅H₃₆F₃N₂O₇, 4.58 (dt, J = 10.8, 7.6 Hz, 130.36, 533.2469; 1H), 4.04-3.96 (m, 127.20 (q, J = 276.2 Hz), found, 1H), 3.94 (s, 3H), 109.48, 83.97, 533.2474 3.87 (dt, J = 9.0, 6.0 Hz, 81.53, 79.02, 1H), 3.65 (dt, J = 9.1, 73.11, 72.07, 6.3 Hz, 1H), 56.07, 51.29, 3.46-3.38 (m, 1H), 33.55, 33.35, 3.33 (dd, J = 9.5, 7.3 Hz, 31.87, 1H), 2.37 (dtd, J = 13.7, 30.90 (q, J = 28.9 Hz), 7.0, 6.1, 2.2 Hz, 28.21, 1H), 2.27-2.04 (m, 23.63, 23.35, 3H), 1.82 (dq, J = 8.2, 23.06 (q, J = 2.8 Hz), 6.3 Hz, 2H), 18.44, 17.90 1.77-1.47 (m, 10H), 1.39 (d, J = 6.4 Hz, 4H), 0.91 (ddt, J = 15.6, 6.0, 1.9 Hz, 1H) F121 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Oil 2936, (m/z) 8.31 (d, J = 8.2 Hz, (CDCl₃) δ 2874, [M + H]⁺ 1H), 8.27 (d, J = 5.5 Hz, 172.69, 1744, calcd for 1H), 6.95 (d, J = 5.5 Hz, 170.29, 1676, C₂₇H₄₁N₂O₉, 1H), 5.74 (s, 162.96, 1501 537.2807; 2H), 4.77 (ddt, J = 12.4, 160.26, found, 7.5, 3.7 Hz, 145.72, 537.2817 1H), 4.66-4.55 (m, 143.98, 1H), 4.06-3.97 (m, 142.43, 1H), 3.91 (s, 3H), 109.57, 89.56, 3.78 (t, J = 7.6, 7.1 Hz, 83.77, 81.76, 1H), 3.55 (td, J = 8.6, 79.17, 75.83, 8.0, 6.3 Hz, 1H), 73.19, 56.18, 3.47-3.37 (m, 1H), 51.63, 33.53, 3.35 (dd, J = 9.5, 7.7 Hz, 33.50, 31.90, 1H), 2.38 (dt, J = 13.7, 28.44, 23.65, 6.8 Hz, 1H), 23.53, 23.34, 2.07 (s, 3H), 20.87, 18.53, 1.79-1.44 (m, 14H), 17.84, 10.66 1.39 (dd, J = 6.5, 1.5 Hz, 3H), 0.93 (t, J = 7.5 Hz, 3H), 0.89-0.82 (m, 1H) F122 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Oil 2954, (m/z) 8.31 (d, J = 8.1 Hz, (CDCl₃) δ 2871, [M + H]⁺ 1H), 8.27 (d, J = 5.2 Hz, 172.79, 1745, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.38, 1676, C₂₇H₄₃N₂O₉, 1H), 5.74 (s, 163.06, 1503 551.2963; 2H), 4.79 (dq, J = 9.2, 160.37, found, 6.5 Hz, 1H), 4.60 (dt, 145.83, 551.2966 J = 10.7, 7.7 Hz, 1H), 144.08, 4.01 (p, J = 4.2 Hz, 142.52, 1H), 3.91 (s, 3H), 109.69, 89.65, 3.65 (dd, J = 8.4, 6.0 Hz, 83.85, 81.89, 1H), 3.43 (t, J = 6.1 Hz, 81.04, 79.23, 1H), 73.35, 56.28, 3.35-3.28 (m, 2H), 51.74, 33.67, 2.37 (dt, J = 13.6, 6.7 Hz, 33.58, 31.99, 1H), 2.07 (s, 3H), 29.27, 28.53, 1.92-1.75 (m, 2H), 23.77, 23.48, 1.65-1.58 (m, 9H), 20.97, 19.71, 1.55-1.44 (m, 2H), 19.50, 18.65, 1.39 (d, J = 6.4 Hz, 18.03 3H), 0.92 (d, J = 6.7 Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H), 0.89-0.83 (m, 1H) F123 Colorless — 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Oil 2957, (m/z) 8.36 (d, J = 8.1 Hz, (CDCl₃) δ 2920, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.36, 2851, calcd for 1H), 6.94 (d, J = 5.5 Hz, 172.80, 1744, C₂₉H₄₅N₂O₉, 1H), 5.81-5.72 (m, 2H), 163.05, 1677, 565.3120; 4.78 (dq, J = 10.2, 6.5 Hz, 160.36, 1503 found, 1H), 4.60 (dt, J = 11.1, 145.71, 565.3131 7.5 Hz, 1H), 144.31, 4.06-3.96 (m, 1H), 142.20, 3.88 (s, 3H), 3.78 (dt, 109.64, 90.03, J = 9.4, 6.6 Hz, 1H), 83.89, 81.88, 3.55 (dt, J = 9.3, 7.0 Hz, 79.28, 75.95, 1H), 3.41 (ddd, J = 7.8, 73.29, 56.25, 5.3, 2.0 Hz, 51.74, 33.97, 1H), 3.32 (dd, J = 9.6, 33.64, 33.62, 7.3 Hz, 1H), 32.02, 28.55, 2.54 (hept, J = 6.7 Hz, 23.77, 23.65, 1H), 2.43-2.31 (m, 23.46, 18.80, 1H), 2.15-2.00 (m, 18.66, 17.96, 1H), 1.81-1.44 (m, 14.24, 10.78 12H), 1.39 (d, J = 6.3 Hz, 2H), 1.36-1.23 (m, 2H), 1.12 (d, J = 8.2 Hz, 6H), 0.92 (t, J = 7.3 Hz, 3H), 0.90-0.83 (m, 1H) F124 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Oil 2954, (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ 2972, [M + H]⁺ 1H), 8.26 (d, J = 5.3 Hz, 176.37, 1744, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.81, 1677, C₃₀H₄₇N₂O₉, 1H), 163.06, 1502 579.3276; 5.81-5.72 (m, 2H), 160.36, found, 4.79 (dt, J = 9.7, 6.3 Hz, 145.71, 579.3287 1H), 4.60 (dt, J = 11.1, 144.32, 7.7 Hz, 1H), 142.21, 4.06-3.96 (m, 1H), 109.64, 90.04, 3.88 (s, 3H), 83.88, 81.92, 3.65 (dd, J = 8.5, 6.0 Hz, 81.06, 79.25, 1H), 3.43 (td, J = 5.5, 73.36, 56.25, 2.8 Hz, 1H), 51.76, 33.97, 3.38-3.26 (m, 2H), 2.54 (h, 33.69, 33.61, J = 7.1 Hz, 1H), 32.01, 29.29, 2.37 (dt, J = 13.6, 6.8 Hz, 28.55, 23.79, 1H), 23.50, 19.73, 2.15-2.01 (m, 1H), 19.53, 18.80, 1.89-1.77 (m, 1H), 18.68, 18.05, 1.77-1.57 (m, 9H), 7.44 1.56-1.47 (m, 1H), 1.39 (d, J = 6.3 Hz, 3H), 1.36-1.29 (m, 1H), 1.14 (d, J = 7.0, 1.6 Hz, 6H), 0.92 (d, J = 6.7 Hz, 3H), 0.90 (d, J = 6.7 Hz, 3H), 0.88-0.81 (m, 1H) F125 White Waxy 34-39 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Solid 2953, (m/z) 8.31 (d, J = 8.1 Hz, (CDCl₃) δ 1749, [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.79, 1677, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.42, 1504 C₂₈H₄₀F₃N₂O₉, 1H), 5.74 (s, 163.11, 605.2680; 2H), 4.77 (dq, J = 9.5, 160.41, found, 6.4 Hz, 1H), 4.60 (dt, 145.86, 605.2688 J = 10.6, 7.6 Hz, 1H), 144.13, 4.00 (ddt, J = 9.1, 5.6, 142.51, 3.4 Hz, 1H), 3.91 (s, 127.35 (d, J = 275.9 Hz), 3H), 3.87 (dt, J = 9.1, 109.74, 89.68, 6.1 Hz, 1H), 3.65 (dt, 84.15, 81.74, J = 9.0, 6.4 Hz, 1H), 79.12, 72.98, 3.41 (ddd, J = 7.2, 72.19, 56.32, 5.1, 1.8 Hz, 1H), 51.75, 33.67, 3.32 (dd, J = 9.5, 7.4 Hz, 33.57, 32.00, 1H), 2.37 (dt, J = 12.4, 31.04 (d, J = 28.9 Hz), 4.5 Hz, 1H), 28.40, 23.77, 2.26-2.09 (m, 2H), 23.48, 2.07 (s, 3H), 23.20 (d, J = 2.6 Hz), 1.86-1.77 (m, 2H), 21.01, 1.77-1.49 (m, 11H), 18.64, 18.03 1.37 (d, J = 6.3 Hz, 3H), 1.36-1.27 (m, 1H), 0.98-0.81 (m, 1H) F126 Colorless — 3386, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR Oil 2925, (m/z) 8.36 (d, J = 8.1 Hz, (CDCl₃) δ 1745, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.39, 1677, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.77, 1503 C₃₀H₄₄F₃N₂O₉, 1H), 163.09, 633.2993; 5.81-5.72 (m, 2H), 160.38, found, 4.78 (dq, J = 9.5, 6.4 Hz, 145.72, 633.3007 1H), 4.60 (dt, J = 10.7, 144.35, 7.6 Hz, 1H), 142.17, 4.07-3.93 (m, 1H), 127.35 (q, J = 276.1 Hz), 3.89 (s, 3H), 109.67, 90.04, 3.88-3.83 (m, 1H), 84.16, 81.74, 3.65 (dt, J = 9.0, 6.3 Hz, 79.11, 72.96, 1H), 3.41 (ddd, J = 7.0, 72.19, 56.26, 5.1, 1.7 Hz, 1H), 51.75, 33.99, 3.32 (dd, J = 9.5, 7.3 Hz, 33.67, 33.58, 1H), 2.55 (hept, J = 7.1 Hz, 32.00, 1H), 31.04 (q, J = 29.1 Hz), 2.43-2.31 (m, 1H), 29.84, 2.26-2.13 (m, 2H), 28.40, 23.77, 2.13-2.02 (m, 1H), 23.49, 1.87-1.76 (m, 2H), 23.20 (q, J = 3.0 Hz), 1.77-1.46 (m, 10H), 18.81, 1.37 (d, J = 6.2 Hz, 3H), 18.64, 18.03 1.32 (ddd, J = 13.5, 8.1, 2.7 Hz, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.93-0.81 (m, 1H) F127 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 12.12-12.02 (m, (CDCl₃) δ [M + H]⁺ 1H), 8.48 (d, J = 8.1 Hz, 171.99, calcd for 1H), 7.99 (d, J = 5.2 Hz, 168.68, C₂₅H₃₃N₂O₇, 1H), 159.70, 473.2282; 7.29-7.25 (m, 2H), 155.36, found, 7.09 (dd, J = 8.8, 1.0 Hz, 148.74, 473.2278 2H), 7.00-6.92 (m, 140.54, 1H), 6.87 (d, J = 5.2 Hz, 130.36, 1H), 5.03 (dq, J = 9.6, 129.35, 6.4 Hz, 1H), 121.35, 4.62 (dt, J = 10.8, 7.6 Hz, 116.48, 1H), 4.42 (dd, J = 9.6, 109.50, 82.98, 7.3 Hz, 1H), 82.91, 72.86, 3.94 (s, 3H), 3.57 (ddd, J = 7.0, 71.40, 56.08, 5.3, 1.6 Hz, 51.31, 33.37, 1H), 3.45 (dt, J = 9.0, 28.11, 23.16, 6.6 Hz, 1H), 3.25 (dt, 18.32, 18.11, J = 9.0, 6.5 Hz, 1H), 10.54 2.42 (ddd, J = 13.9, 10.0, 4.4 Hz, 1H) 2.32-2.13 (m, 1H), 1.77 (dq, J = 10.2, 6.5, 5.2 Hz, 2H), 1.50-1.39 (m, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.06 (dd, J = 16.1, 7.2 Hz, 1H), 0.77 (t, J = 7.4 Hz, 3H) F128 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.06 (d, J = 0.5 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.49 (d, J = 8.1 Hz, 171.98, calcd for 1H), 7.99 (d, J = 5.2 Hz, 168.69, C₃₁H₃₇N₂O₇, 1H), 159.66, 549.2595; 7.31-7.20 (m, 4H), 155.37, found, 7.19-7.07 (m, 3H), 148.75, 549.2602 7.06-7.01 (m, 2H), 142.00, 6.99-6.92 (m, 1H), 6.87 (d, 140.55, J = 5.2 Hz, 1H), 130.36, 5.04 (dq, J = 9.6, 6.4 Hz, 129.43, 1H), 4.63 (dt, J = 10.8, 128.41, 7.6 Hz, 1H), 128.21, 4.47 (dd, J = 9.6, 7.4 Hz, 125.65, 1H), 3.94 (s, 3H), 121.40, 3.61-3.49 (m, 2H), 116.35, 3.27 (dt, J = 9.2, 6.2 Hz, 109.51, 83.12, 1H), 82.54, 72.86, 2.55-2.46 (m, 2H), 2.42 (dt, J = 13.7, 68.59, 56.09, 6.7 Hz, 1H), 51.30, 33.37, 2.27-2.13 (m, 1H), 32.17, 31.54, 1.88-1.67 (m, 4H), 28.01, 18.31, 1.49-1.39 (m, 1H), 18.10 1.37 (d, J = 6.4 Hz, 3H), 1.05 (dd, J = 16.1, 7.5 Hz, 1H) F129 White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Crystalline (m/z) 12.05 (d, J = 0.5 Hz, (CDCl₃) δ Solid [M + H]⁺ 1H), 8.48 (d, J = 8.1 Hz, 171.93, calcd for 1H), 8.00 (d, J = 5.2 Hz, 168.70, C₂₆H₃₂F₃N₂O₇, 1H), 7.28 (dd, 159.35, 541.2156; J = 8.4, 7.0 Hz, 2H), 155.38, found, 7.04 (dd, J = 8.8, 0.9 Hz, 148.75, 541.2158 2H), 140.55, 7.00-6.93 (m, 1H), 6.87 (d, J = 5.2 Hz, 130.33, 1H), 5.04 (dq, 129.46, J = 9.6, 6.4 Hz, 1H), 127.18 (q, J = 276.1 Hz), 4.64 (dt, J = 10.8, 7.6 Hz, 121.52, 1H), 4.46 (dd, J = 9.6, 116.03, 7.4 Hz, 1H), 109.52, 83.40, 3.94 (s, 3H), 3.56 (td, J = 6.1, 82.07, 72.69, 5.3, 3.5 Hz, 2H), 67.61, 56.08, 3.28 (dt, J = 9.1, 6.0 Hz, 51.25, 33.29, 1H), 2.42 (dt, J = 13.8, 30.43 (q, J = 28.9 Hz), 6.7 Hz, 1H), 28.00, 2.19 (dddd, J = 15.8, 22.59 (q, J = 2.9 Hz), 10.1, 8.2, 5.3 Hz, 18.25, 1H), 1.96-1.70 (m, 18.02 4H), 1.66-1.58 (m, 2H), 1.50-1.40 (m, 1H), 1.38 (d, J = 6.4 Hz, 3H), 1.08 (dd, J = 16.2, 7.5 Hz, 1H) F130 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.59, calcd for 1H), 170.29, C₃₄H₄₁N₂O₉, 7.30-7.24 (m, 2H), 7.21 (t, J = 7.2 Hz, 163.01, 621.2807; 2H), 7.14 (dd, 160.27, found, J = 8.5, 6.0 Hz, 1H), 157.57, 621.2809 7.08 (d, J = 7.0 Hz, 145.75, 2H), 7.00-6.89 (m, 144.00, 4H), 5.74 (s, 2H), 142.35, 4.92 (dq, J = 9.7, 6.3 Hz, 141.94, 1H), 4.65 (dt, J = 10.7, 129.54, 7.6 Hz, 1H), 128.34, 4.40 (t, J = 5.6 Hz, 128.26, 1H), 3.90 (s, 3H), 125.69, 3.79 (dt, J = 9.1, 6.3 Hz, 121.27, 1H), 116.58, 3.74-3.59 (m, 2H), 109.65, 89.52, 2.63-2.52 (m, 2H), 2.36 (dt, J = 13.7, 83.56, 82.89, 7.0 Hz, 1H), 73.07, 72.71, 2.27-2.10 (m, 1H), 56.20, 51.59, 2.07 (s, 3H), 33.27, 32.32, 1.81 (dd, J = 14.4, 5.6 Hz, 31.88, 28.28, 3H), 1.64 (dt, J = 15.5, 20.89, 18.27, 7.6 Hz, 1H), 18.01 1.46 (d, J = 6.4 Hz, 3H), 1.37-1.23 (m, 1H), 1.06 (dd, J = 16.0, 7.7 Hz, 1H) F131 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.52 (d, J = 7.4 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.47, calcd for 1H), 168.90, C₃₃H₃₉N₂O₈, 7.30-7.11 (m, 5H), 162.44, 591.2701; 7.10-7.04 (m, 2H), 159.45, found, 7.00-6.89 (m, 4H), 4.92 (dq, J = 9.7, 157.57, 591.2706 6.3 Hz, 1H), 146.72, 4.64 (dt, J = 10.7, 7.7 Hz, 141.94, 1H), 4.39 (t, J = 5.5 Hz, 141.35, 1H), 3.88 (s, 3H), 137.51, 3.79 (dt, J = 9.1, 6.3 Hz, 129.55, 1H), 128.35, 3.70-3.59 (m, 2H), 128.27, 2.62-2.52 (m, 2H), 2.40 (s, 3H), 125.70, 2.38-2.28 (m, 1H), 121.28, 2.23-2.09 (m, 1H), 116.58, 1.86-1.75 (m, 3H), 109.85, 83.56, 1.61 (dq, J = 15.6, 82.90, 73.07, 7.6 Hz, 1H), 1.45 (d, 72.73, 56.30, J = 6.4 Hz, 3H), 51.31, 33.50, 1.28 (q, J = 11.1 Hz, 1H), 32.33, 31.89, 1.05 (dd, J = 16.1, 28.31, 20.77, 7.8 Hz, 1H) 18.24, 17.99 F132 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.50 (d, J = 7.2 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.47, calcd for 1H), 169.44, C₃₅H₄₃N₂O₉, 7.30-7.12 (m, 5H), 162.39, 635.2963; 7.11-7.05 (m, 2H), 159.45, found, 7.00-6.88 (m, 4H), 4.92 (dq, J = 9.7, 157.57, 635.2977 6.4 Hz, 1H), 146.77, 4.63 (dt, J = 10.6, 7.7 Hz, 141.94, 1H), 4.39 (t, J = 5.5 Hz, 141.39, 1H), 3.88 (s, 3H), 137.36, 3.85-3.74 (m, 3H), 129.54, 3.72-3.57 (m, 2H), 128.35, 3.41 (s, 3H), 2.98 (t, 128.26, J = 6.6 Hz, 2H), 125.70, 2.61-2.53 (m, 2H), 121.28, 2.33 (dt, J = 13.7, 7.0 Hz, 116.58, 1H), 2.24-2.08 (m, 109.84, 83.56, 1H), 1.83-1.75 (m, 82.90, 73.06, 3H), 1.61 (dq, J = 16.1, 72.70, 67.59, 7.7 Hz, 1H), 58.80, 56.33, 1.45 (d, J = 6.4 Hz, 51.29, 34.64, 3H), 1.35-1.20 (m, 33.49, 32.32, 1H), 1.05 (dd, J = 16.1, 31.88, 28.29, 7.8 Hz, 1H) 18.24, 17.99 F133 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.60, calcd for 1H), 170.30, C₃₄H₄₁N₂O₉, 7.32-7.26 (m, 2H), 7.22 (ddd, J = 7.5, 163.00, 621.2807; 6.4, 1.2 Hz, 160.28, found, 2H), 7.17-7.07 (m, 159.70, 621.2809 3H), 7.06-7.01 (m, 145.74, 2H), 6.99-6.93 (m, 144.03, 2H), 5.74 (s, 2H), 142.36, 5.02 (dq, J = 9.6, 6.4 Hz, 142.03, 1H), 4.65 (dt, J = 10.7, 129.41, 7.6 Hz, 1H), 128.42, 4.46 (dd, J = 9.6, 7.4 Hz, 128.20, 1H), 3.90 (s, 3H), 125.63, 3.61-3.48 (m, 2H), 121.35, 3.26 (dt, J = 9.2, 6.2 Hz, 116.35, 1H), 109.65, 89.53, 2.54-2.47 (m, 2H), 2.43 (dt, J = 13.6, 83.20, 82.60, 6.8 Hz, 1H), 72.59, 68.54, 2.26-2.10 (m, 1H), 56.20, 51.65, 2.07 (s, 3H), 33.43, 32.17, 1.86-1.65 (m, 4H), 31.55, 28.08, 1.45-1.30 (m, 4H), 20.89, 18.38, 1.05 (dd, J = 16.1, 7.6 Hz, 18.10 1H) F134 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.54 (d, J = 7.4 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 172.48, calcd for 1H), 168.91, C₃₃H₃₉N₂O₈, 7.30-7.20 (m, 4H), 162.43, 591.2701; 7.17-7.06 (m, 3H), 159.69, found, 7.06-6.92 (m, 4H), 5.01 (dq, J = 9.6, 159.46, 591.2705 6.4 Hz, 1H), 146.71, 4.64 (dt, J = 10.7, 7.6 Hz, 142.02, 1H), 4.44 (dd, J = 9.6, 141.38, 7.4 Hz, 1H), 137.52, 3.89 (s, 3H), 129.41, 3.61-3.47 (m, 2H), 3.25 (dt, J = 9.2, 128.42, 6.2 Hz, 1H), 128.21, 2.54-2.47 (m, 2H), 125.64, 2.40 (s, 4H), 121.36, 2.25-2.11 (m, 1H), 116.36, 1.80-1.68 (m, 4H), 109.85, 83.20, 1.41-1.29 (m, 4H), 1.04 (dd, J = 16.1, 82.60, 72.61, 7.5 Hz, 1H) 68.55, 56.30, 51.37, 33.66, 32.17, 31.54, 28.09, 20.76, 18.35, 18.08 F135 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.54, calcd for 1H), 170.30, C₂₉H₃₆F₃N₂O₉, 7.32-7.24 (m, 2H), 163.00, 613.2367; 7.08-7.00 (m, 2H), 160.28, found, 6.99-6.92 (m, 2H), 5.74 (s, 2H), 159.38, 613.2378 5.02 (dq, J = 9.6, 6.4 Hz, 145.74, 1H), 4.65 (dt, J = 10.7, 144.03, 7.6 Hz, 1H), 142.31, 4.45 (dd, J = 9.6, 7.4 Hz, 129.44, 1H), 3.91 (s, 3H), 127.19 (q, J = 276.1 Hz), 3.57 (dt, J = 10.7, 5.7 Hz, 121.46, 2H), 3.27 (dt, J = 9.2, 116.03, 6.0 Hz, 1H), 109.66, 89.50, 2.43 (dt, J = 13.6, 6.8 Hz, 83.46, 82.12, 1H), 2.26-2.11 (m, 72.41, 67.56, 1H), 2.07 (s, 3H), 56.19, 51.60, 1.87 (dtt, J = 22.6, 33.34, 11.3, 3.2 Hz, 2H), 30.43 (q, J = 28.8 Hz), 1.80-1.67 (m, 2H), 28.05, 1.62 (ddd, J = 14.0, 22.58 (q, J = 2.8 Hz), 7.8, 6.4 Hz, 2H), 20.87, 1.45-1.32 (m, 4H), 18.32, 18.01 1.08 (dd, J = 16.1, 7.6 Hz, 1H) F136 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.39 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.25, calcd for 1H), 172.53, C₃₁H₄₀F₃N₂O₈, 7.31-7.24 (m, 2H), 162.98, 641.2680; 7.07-7.00 (m, 2H), 160.25, found, 7.00-6.92 (m, 2H), 159.39, 641.2687 5.80-5.73 (m, 2H), 5.02 (dq, J = 9.6, 145.60, 6.4 Hz, 1H), 144.23, 4.65 (dt, J = 10.7, 7.6 Hz, 141.97, 1H), 4.45 (dd, J = 9.6, 129.43, 7.4 Hz, 1H), 127.19 (q, J = 276.1 Hz), 3.89 (s, 3H), 3.57 (dt, J = 10.8, 121.45, 5.7 Hz, 2H), 116.03, 3.27 (dt, J = 9.1, 6.0 Hz, 109.60, 89.86, 1H), 2.55 (hept, J = 7.0 Hz, 83.47, 82.13, 1H), 72.39, 67.56, 2.42 (dt, J = 13.7, 6.8 Hz, 56.14, 51.59, 1H), 2.27-2.07 (m, 33.85, 33.34, 1H), 1.87 (dddd, J = 22.2, 30.43 (q, J = 28.8 Hz), 11.1, 7.8, 3.1 Hz, 28.04, 2H), 22.58 (q, J = Hz), 1.78-1.57 (m, 4H), 1.36 (d, J = 6.4 Hz, 18.67, 4H), 1.14 (d, 18.32, 18.01 J = 7.0 Hz, 6H), 1.08 (dd, J = 16.2, 7.6 Hz, 1H) F137 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.54 (d, J = 7.7 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 172.42, calcd for 1H), 168.90, C₂₈H₃₄F₃N₂O₈, 7.32-7.22 (m, 2H), 162.43, 583.2262; 7.05-6.99 (m, 3H), 159.46, found, 6.99-6.93 (m, 1H), 5.01 (dq, J = 9.6, 159.38, 583.2272 6.4 Hz, 1H), 146.71, 4.64 (dt, J = 10.7, 7.6 Hz, 141.33, 1H), 4.43 (dd, J = 9.6, 137.52, 7.4 Hz, 1H), 129.44, 3.90 (s, 3H), 3.56 (dt, J = 10.7, 127.19 (q, J = 276.1 Hz), 5.7 Hz, 2H), 121.46, 3.26 (dt, J = 9.1, 6.0 Hz, 116.03, 1H), 2.40 (s, 4H), 109.86, 83.46, 2.22-2.10 (m, 1H), 82.11, 72.42, 1.85 (dtdd, J = 22.1, 67.57, 56.29, 11.0, 7.6, 3.1 Hz, 51.32, 33.56, 2H), 1.77-1.56 (m, 30.43 (q, J = 28.8 Hz), 4H), 1.35 (d, J = 6.4 Hz, 28.07, 4H), 1.07 (dd, J = 16.2, 22.57 (q, J = 2.9 Hz), 7.5 Hz, 1H) 20.74, 18.28, 18.00 F138 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.60, calcd for 1H), 7.27 (t, J = 8.0 Hz, 170.28, C₂₈H₃₇N₂O₉, 2H), 7.09 (d, 162.99, 545.2494; J = 7.9 Hz, 2H), 160.27, found, 7.00-6.91 (m, 2H), 159.72, 545.2511 5.74 (s, 2H), 5.01 (dq, J = 9.6, 145.73, 6.4 Hz, 1H), 144.01, 4.64 (dt, J = 10.7, 7.6 Hz, 142.35, 1H), 4.41 (dd, J = 9.6, 129.32, 7.3 Hz, 1H), 121.30, 3.91 (s, 3H), 3.56 (t, J = 5.5 Hz, 116.48, 1H), 3.45 (dt, 109.64, 89.52, J = 9.0, 6.6 Hz, 1H), 83.04, 82.96, 3.24 (dt, J = 9.0, 6.5 Hz, 72.58, 71.36, 1H), 2.42 (dt, J = 13.8, 56.19, 51.65, 6.6 Hz, 1H), 33.42, 28.17, 2.19 (ddd, J = 15.7, 23.15, 20.87, 8.9, 4.5 Hz, 1H), 18.38, 18.10, 2.07 (s, 3H), 10.54 1.82-1.64 (m, 2H), 1.50-1.32 (m, 6H), 1.05 (dd, J = 16.1, 7.3 Hz, 1H), 0.77 (t, J = 7.4 Hz, 3H) F139 Clear Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil (m/z) 8.39 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.24, calcd for 1H), 172.59, C₃₀H₄₁N₂O₉, 7.31-7.22 (m, 2H), 162.96, 573.2807; 7.12-7.05 (m, 2H), 160.25, found, 7.00-6.91 (m, 2H), 159.73, 573.2819 5.81-5.73 (m, 2H), 5.01 (dq, J = 9.6, 145.59, 6.4 Hz, 1H), 144.22, 4.64 (dt, J = 10.8, 7.6 Hz, 142.01, 1H), 4.42 (dd, J = 9.6, 129.32, 7.3 Hz, 1H), 121.29, 3.88 (s, 3H), 3.56 (ddd, J = 7.0, 116.48, 5.2, 1.5 Hz, 109.58, 89.87, 1H), 3.50-3.41 (m, 83.04, 82.97, 1H), 3.24 (dt, J = 9.0, 72.56, 71.35, 6.5 Hz, 1H), 56.14, 51.64, 2.55 (hept, J = 7.0 Hz, 33.84, 33.42, 1H), 2.42 (dt, J = 13.9, 28.17, 23.15, 6.6 Hz, 1H), 18.67, 18.39, 2.27-2.12 (m, 1H), 18.10, 10.54 1.74 (ddd, J = 15.3, 11.6, 7.7 Hz, 2H), 1.48-1.32 (m, 6H), 1.14 (d, J = 7.0 Hz, 6H), 1.05 (dd, J = 16.1, 7.3 Hz, 1H), 0.77 (t, J = 7.4 Hz, 3H) F140 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.51 (d, J = 7.1 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 172.49, calcd for 1H), 169.43, C₂₉H₃₉N₂O₉, 7.31-7.23 (m, 2H), 162.37, 559.2650; 7.10-7.03 (m, 2H), 6.99 (d, J = 5.5 Hz, 159.72, found, 1H), 159.45, 559.2666 6.98-6.92 (m, 1H), 146.76, 5.01 (dq, J = 9.7, 6.4 Hz, 141.40, 1H), 4.62 (dt, J = 10.7, 137.35, 7.7 Hz, 1H), 129.33, 4.40 (dd, J = 9.6, 7.3 Hz, 121.30, 1H), 3.89 (s, 3H), 116.48, 3.81 (t, J = 6.6 Hz, 109.84, 83.04, 2H), 3.55 (dd, J = 8.9, 82.96, 72.58, 3.5 Hz, 1H), 71.36, 67.56, 3.49-3.35 (m, 4H), 58.77, 56.32, 3.23 (dt, J = 9.0, 6.5 Hz, 51.35, 34.61, 1H), 2.98 (t, J = 6.6 Hz, 33.61, 28.17, 2H), 2.38 (dt, J = 13.8, 23.14, 18.35, 6.4 Hz, 1H), 18.08, 10.53 2.18 (ddt, J = 15.6, 8.5, 5.0 Hz, 1H), 1.71 (dq, J = 18.0, 7.7, 7.0 Hz, 2H), 1.49-1.27 (m, 6H), 1.04 (dd, J = 16.1, 7.2 Hz, 1H), 0.76 (t, J = 7.4 Hz, 3H) F141 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.54 (d, J = 7.7 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 172.49, calcd for 1H), 168.90, C₂₇H₃₅N₂O₈, 7.30-7.24 (m, 2H), 7.08 (dd, J = 8.8, 162.41, 515.2388; 1.0 Hz, 2H), 159.72, found, 7.00 (d, J = 5.5 Hz, 1H), 159.44, 515.2397 6.98-6.92 (m, 1H), 146.71, 5.01 (dq, J = 9.7, 6.4 141.37, Hz, 1H), 4.63 (dt, J = 10.7, 137.50, 7.5 Hz, 1H), 129.33, 4.40 (dd, J = 9.6, 7.3 Hz, 121.30, 1H), 3.90 (s, 3H), 116.49, 3.55 (ddd, J = 7.0, 109.84, 83.05, 5.2, 1.5 Hz, 1H), 82.96, 72.60, 3.45 (dt, J = 9.0, 6.6 Hz, 71.38, 56.29, 1H), 3.23 (dt, J = 9.0, 51.37, 33.64, 6.5 Hz, 1H), 2.39 (s, 28.19, 23.14, 4H), 2.26-2.12 (m, 20.74, 18.35, 1H), 1.81-1.66 (m, 18.09, 10.53 2H), 1.49-1.29 (m, 6H), 1.04 (dd, J = 16.1, 7.2 Hz, 1H), 0.76 (t, J = 7.4 Hz, 3H) F142 White Solid 69-72 3364, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2946, (m/z) 12.06 (s, 1H), (CDCl₃) δ 1733, [M + H]⁺ 8.44 (d, J = 8.0 Hz, 1H), 173.89, 1649, calcd for 7.99 (d, J = 5.2 Hz, 172.14, 1527 C₂₅H₃₅N₂O₈, 1H), 6.87 (d, J = 5.3 Hz, 168.65, 491.2388; 1H), 5.07 (dd, J = 9.8, 155.36, found, 7.7 Hz, 1H), 148.74, 491.2393 4.98 (dq, J = 9.8, 6.3 Hz, 140.50, 1H), 4.61 (dt, J = 10.7, 130.35, 7.6 Hz, 1H), 109.48, 79.51, 3.96-3.90 (m, 1H), 78.43, 75.63, 3.94 (s, 3H), 71.82, 56.08, 3.45 (ddd, J = 7.5, 5.4, 2.0 Hz, 51.34, 33.32, 1H), 2.40 (dtd, J = 13.4, 33.21, 32.01, 7.1, 1.4 Hz, 28.73, 23.44, 1H), 2.13 (dddd, J = 15.7, 23.15, 18.22, 10.0, 7.8, 5.4 Hz, 17.32, 12.79, 1H), 8.46, 8.42 1.92-1.35 (m, 13H), 1.30 (d, J = 6.2 Hz, 3H), 1.12-1.00 (m, 3H), 0.93-0.84 (m, 2H) F143 White Solid 124-125 3376, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2950, (m/z) 12.06 (s, 1H), (CDCl₃) δ 2870, [M + H]⁺ 8.44 (d, J = 8.0 Hz, 1H), 175.57, 1734, calcd for 7.99 (d, J = 5.2 Hz, 172.14, 1652, C₂₇H₃₉N₂O₈, 1H), 6.87 (d, J = 5.2 Hz, 168.65, 1527 519.2701; 1H), 5.09 (dd, J = 9.7, 155.36, found, 7.7 Hz, 1H), 148.74, 519.2709 4.97 (dq, J = 9.7, 6.3 Hz, 140.49, 1H), 4.62 (dt, J = 10.7, 130.35, 7.6 Hz, 1H), 109.48, 79.38, 3.94 (s, 3H), 78.55, 75.37, 3.93-3.88 (m, 1H), 71.87, 56.07, 3.46 (ddd, J = 7.5, 5.4, 1.9 Hz, 51.32, 43.98, 1H), 2.74 (p, J = 8.0 Hz, 33.30, 33.27, 1H), 32.08, 30.31, 2.40 (ddd, J = 12.4, 7.5, 29.74, 28.54, 6.1 Hz, 1H), 25.82, 25.73, 2.22-2.07 (m, 1H), 23.49, 23.27, 2.01-1.34 (m, 19H), 18.20, 17.32 1.28 (d, J = 6.3 Hz, 3H), 1.02 (ddt, J = 16.2, 7.9, 2.1 Hz, 1H) F144 White Solid 39-43 3380, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2953, (m/z) 8.30 (d, J = 7.9 Hz, (CDCl₃)δ 1735, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 173.86, 1678, calcd for 1H), 6.96 (d, J = 5.4 Hz, 172.72, 1503 C₂₈H₃₉N₂O₁₀, 1H), 5.73 (s, 170.27, 563.2599; 2H), 5.06 (dd, J = 9.8, 162.94, found, 7.7 Hz, 1H), 4.96 (dq, 160.27, 563.2605 J = 9.7, 6.3 Hz, 1H), 145.68, 4.62 (dt, J = 10.8, 7.5 Hz, 144.03, 1H), 142.28, 3.96-3.92 (m, 1H), 3.91 (s, 3H), 109.62, 89.52, 3.44 (ddd, J = 7.6, 79.47, 78.48, 5.4, 2.0 Hz, 1H), 75.71, 71.51, 2.40 (dt, J = 13.4, 6.4 Hz, 56.18, 51.67, 1H), 2.21-2.09 (m, 33.36, 33.18, 1H), 2.07 (s, 3H), 31.99, 29.68, 1.81-1.44 (m, 10H), 28.82, 23.43, 1.36 (dtd, J = 12.9, 23.14, 20.85, 11.2, 1.6 Hz, 1H), 18.30, 17.30, 1.29 (d, J = 6.2 Hz, 12.78, 8.42 3H), 1.09-0.98 (m, 3H), 0.93-0.79 (m, 3H) F145 White Solid 48-51 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2946, (m/z) 8.35 (d, J = 8.0 Hz, (CDCl₃) δ 2875, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.25, 17334, calcd for 1H), 6.94 (d, J = 5.4 Hz, 173.86, 1676, C₃₀H₄₃N₂O₁₀, 1H), 172.73, 1503 591.2912; 5.80-5.72 (m, 2H), 162.92, found, 5.06 (dd, J = 9.8, 7.7 Hz, 160.25, 591.2918 1H), 4.96 (dq, J = 9.7, 145.55, 6.2 Hz, 1H), 144.26, 4.62 (dt, J = 10.7, 7.5 Hz, 141.97, 1H), 3.95-3.88 (m, 109.55, 89.90, 1H), 3.89 (s, 3H), 79.47, 78.48, 3.44 (ddd, J = 7.6, 75.72, 71.51, 5.5, 2.0 Hz, 1H), 56.13, 53.44, 2.55 (hept, J = 7.0 Hz, 51.67, 33.83, 1H), 2.40 (dtd, J = 13.4, 33.38, 33.19, 7.2, 1.5 Hz, 32.00, 28.84, 1H), 2.20-2.04 (m, 23.43, 23.14, 1H), 1.81-1.44 (m, 18.66, 18.31, 11H), 1.44-1.31 (m, 17.31, 12.78, 1H), 1.29 (d, J = 6.2 Hz, 8.42, 8.37 3H), 1.14 (d, J = 7.0 Hz, 6H), 1.08-0.97 (m, 3H), 0.92-0.85 (m, 2H) F146 White Solid 144-145 2955, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 1770, (m/z) 8.54-8.47 (m, 1H), (CDCl₃) δ 1745, [M + H]⁺ 8.32 (d, J = 5.4 Hz, 172.56, 1680, calcd for 1H), 6.99 (d, J = 5.5 Hz, 169.39, 1509 C₂₉H₄₅N₂O₉, 1H), 4.78 (dq, J = 9.5, 162.31, 565.3120; 6.3 Hz, 1H), 159.41, found, 4.58 (ddd, J = 10.7, 8.5, 146.72, 565.3124 7.3 Hz, 1H), 141.43, 4.00 (ddt, J = 6.6, 4.2, 2.6 Hz, 137.30, 1H), 3.89 (s, 3H), 109.77, 83.72, 3.81 (t, J = 6.6 Hz, 81.78, 80.91, 2H), 3.65 (dd, J = 8.5, 79.11, 73.22, 5.9 Hz, 1H), 67.56, 58.76, 3.45-3.41 (m, 1H), 56.30, 51.32, 3.40 (s, 3H), 3.30 (dt, J = 9.7, 34.61, 33.66, 7.4 Hz, 2H), 33.55, 31.87, 2.98 (t, J = 6.6 Hz, 2H), 29.15, 28.41, 2.40-2.28 (m, 1H), 23.65, 23.36, 2.07 (dddd, J = 15.7, 19.59, 19.39, 10.0, 8.3, 5.1 Hz, 18.50, 17.90 1H), 1.83 (dt, J = 13.2, 6.7 Hz, 1H), 1.76-1.45 (m, 10H), 1.38 (d, J = 6.4 Hz, 3H), 1.35-1.25 (m, 1H), 0.92 (d, J = 6.6 Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H; 0.90-0.85 (m, 1H) F147 White Solid 44-47 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2951, (m/z) 8.52-8.45 (m, 1H), (CDCl₃) δ 1735, [M + H]⁺ 8.32 (d, J = 5.4 Hz, 173.85, 1679, calcd for 1H), 7.00 (d, J = 5.5 Hz, 172.61, 1508 C₂₉H₄₁N₂O₁₀, 1H), 5.05 (dd, J = 9.8, 169.40, 577.2756; 7.7 Hz, 1H), 162.30, found, 4.95 (dq, J = 9.8, 6.3 Hz, 159.44, 577.2761 1H), 4.61 (dt, J = 10.6, 146.71, 7.6 Hz, 1H), 141.38, 3.92 (dq, J = 5.1, 2.7, 137.34, 2.1 Hz, 1H), 3.89 (s, 109.82, 79.47, 3H), 3.81 (t, J = 6.5 Hz, 78.48, 75.69, 2H), 3.44 (dq, J = 5.8, 71.51, 67.55, 3.6, 2.8 Hz, 1H), 58.76, 56.31, 3.40 (s, 3H), 2.98 (t, J = 6.6 Hz, 51.34, 34.61, 2H), 33.61, 33.18, 2.42-2.31 (m, 1H), 31.99, 28.82, 2.11 (dddd, J = 15.7, 9.9, 23.43, 23.14, 8.2, 4.1 Hz, 1H), 18.27, 17.28, 1.82-1.42 (m, 10H), 12.77, 8.42, 1.41-1.30 (m, 1H), 8.37 1.27 (d, J = 6.3 Hz, 3H), 1.06-0.97 (m, 3H), 0.91-0.82 (m, 3H) F148 White Solid 48-51 3371, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2952, (m/z) 8.30 (d, J = 8.0 Hz, (CDCl₃) δ 2871, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 175.52, 1737, calcd for 1H), 6.96 (d, J = 5.4 Hz, 172.72, 1676, C₃₀H₄₃N₂O₁₀, 1H), 5.74 (s, 170.26, 1504 591.2912; 2H), 5.08 (dd, J = 9.8, 162.94, found, 7.7 Hz, 1H), 160.27, 591.2936 4.95 (dq, J = 9.7, 6.3 Hz, 145.68, 1H), 4.63 (dt, J = 10.8, 144.05, 7.5 Hz, 1H), 142.28, 3.95-3.85 (m, 1H), 109.62, 89.53, 3.91 (s, 3H), 79.33, 78.60, 3.45 (ddd, J = 7.6, 5.4, 1.9 Hz, 75.44, 71.55, 1H), 2.73 (p, J = 8.0 Hz, 56.18, 51.65, 1H), 43.97, 33.36, 2.46-2.34 (m, 1H), 33.25, 32.06, 2.21-2.09 (m, 1H), 2.07 (s, 30.29, 29.72, 3H), 1.99-1.44 (m, 28.63, 25.80, 18H), 1.43-1.30 (m, 25.74, 23.48, 1H), 1.27 (d, J = 6.4 Hz, 23.26, 20.85, 3H), 1.02 (ddt, J = 16.1, 18.28, 17.31 7.9, 2.3 Hz, 1H) F149 White Foam — 3368, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 12.06 (s, 1H), (CDCl₃) δ 2871, [M + H]⁺ 8.44 (d, J = 8.1 Hz, 1H), 175.59, 1737, calcd for 7.99 (d, J = 5.1 Hz, 172.12, 1528 C₂₆H₃₉N₂O₈, 1H), 6.87 (d, J = 5.2 Hz, 168.66, 507.2701; 1H), 5.17 (dd, J = 9.7, 155.37, found, 7.8 Hz, 1H), 148.75, 507.2717 4.97 (dq, J = 9.7, 6.4 Hz, 140.50, 1H), 4.62 (dt, J = 10.9, 130.36, 7.6 Hz, 1H), 109.48, 81.11, 3.94 (s, 3H), 76.14, 75.26, 3.39 (ddd, J = 7.6, 5.3, 1.9 Hz, 71.77, 56.08, 1H), 3.27 (dd, J = 8.7, 51.28, 43.97, 6.3 Hz, 1H), 33.30, 30.13, 2.98 (dd, J = 8.7, 6.6 Hz, 29.77, 28.69, 1H), 2.74 (p, J = 8.0 Hz, 27.73, 25.82, 1H), 25.72, 19.37, 2.47-2.33 (m, 1H), 19.33, 17.95, 2.26-2.10 (m, 1H), 17.26 1.96-1.64 (m, 9H), 1.64-1.52 (m, 2H), 1.41 (dtd, J = 13.2, 11.6, 1.6 Hz, 1H), 1.29 (d, J = 6.4 Hz, 3H), 1.01 (ddt, J = 16.3, 8.0, 2.0 Hz, 1H), 0.85 (d, J = 6.7 Hz, 6H) F150 White Foam — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 8.30 (d, J = 7.8 Hz, (CDCl₃) δ 2872, [M + Na]⁺ 1H), 8.27 (d, J = 5.3 Hz, 175.56, 1739, calcd for 1H), 6.95 (d, J = 5.4 Hz, 172.74, 1503 C₂₉H₄₂N₂NaO₁₀, 1H), 5.74 (s, 170.33, 601.2732; 2H), 5.16 (dd, J = 9.8, 162.95, found, 7.8 Hz, 1H), 160.29, 01.2758 4.95 (dq, J = 9.8, 6.4 Hz, 145.68, 1H), 4.64 (dt, J = 10.8, 144.11, 7.6 Hz, 1H), 142.32, 3.91 (s, 3H), 109.60, 89.59, 3.37 (ddd, J = 7.5, 5.3, 1.9 Hz, 81.19, 76.12, 1H), 3.27 (dd, J = 8.7, 75.36, 71.49, 6.3 Hz, 1H), 56.19, 51.62, 2.97 (dd, J = 8.7, 6.6 Hz, 43.98, 33.39, 1H), 2.73 (p, J = 7.9 Hz, 30.13, 29.76, 1H), 2.41 (dt, J = 13.8, 28.69, 27.84, 7.1 Hz, 1H), 25.82, 25.72, 2.24-2.09 (m, 1H), 20.89, 19.37, 2.08 (s, 3H), 19.34, 18.04, 1.95-1.61 (m, 11H), 17.27 1.42-1.29 (m, 1H), 1.27 (d, J = 6.4 Hz, 3H), 1.07-0.96 (m, 1H), 0.85 (d, J = 6.7 Hz, 6H) F151 White Foam — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2955, (m/z) 8.50 (d, J = 8.2 Hz, (CDCl₃) δ 2872, [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 175.57, 1738 calcd for 1H), 7.00 (d, J = 5.5 Hz, 172.62, C₂₈H₄₁N₂O₉, 1H), 5.14 (dd, 168.93, 549.2807; J = 9.8, 7.8 Hz, 1H), 162.36, found, 4.99-4.91 (m, 1H), 159.45, 549.2832 4.63 (dt, J = 10.8, 7.7 Hz, 146.66, 1H), 3.91 (s, 3H), 141.39, 3.39-3.35 (m, 1H), 137.52, 3.26 (dd, J = 8.7, 6.2 Hz, 109.80, 81.19, 1H), 2.96 (dd, J = 8.7, 76.13, 75.34, 6.6 Hz, 1H), 71.50, 56.29, 2.77-2.69 (m, 1H), 51.33, 43.98, 2.42-2.35 (m, 1H), 2.40 (s, 33.62, 30.13, 3H), 2.23-2.08 (m, 29.76, 28.68, 1H), 1.97-1.60 (m, 27.86, 25.82, 11H), 1.38-1.27 (m, 25.72, 20.76, 1H), 1.26 (d, J = 6.4 Hz, 19.37, 19.33, 3H), 1.00 (dd, J = 15.7, 18.0, 17.24 7.7 Hz, 1H), 0.85 (dd, J = 6.7, 2.6 Hz, 6H) F152 White Foam — 3378, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 8.47 (s, 1H), 8.33 (d, (CDCl₃) δ 2872, [M + H]⁺ J = 5.4 Hz, 1H), 175.58, 1738 calcd for 6.99 (d, J = 5.4 Hz, 1H), 172.63, C₃₀H₄₅N₂O₁₀, 5.14 (dd, J = 9.8, 7.8 Hz, 169.47, 593.3069; 1H), 4.94 (dq, J = 9.7, 162.32, found, 6.3 Hz, 1H), 159.46, 593.3077 4.62 (dt, J = 10.8, 7.7 Hz, 146.71, 1H), 3.90 (s, 3H), 141.42, 3.81 (t, J = 6.6 Hz, 137.38, 2H), 3.41 (s, 3H), 109.79, 81.19, 3.37 (ddd, J = 7.5, 76.12, 75.33, 5.2, 1.9 Hz, 1H), 71.49, 67.57, 3.26 (dd, J = 8.7, 6.3 Hz, 58.80, 56.32, 1H), 3.01-2.94 (m, 51.31, 43.98, 2H), 2.73 (p, J = 7.9 Hz, 34.62, 33.62, 1H), 2.37 (dt, J = 13.6, 30.13, 29.76, 7.0 Hz, 1H), 28.68, 27.83, 2.23-2.06 (m, 1H), 25.82, 25.72, 1.96-1.50 (m, 12H), 19.37, 19.33, 1.39-1.29 (m, 1H), 18.00, 17.23 1.26 (d, J = 6.3 Hz, 3H), 1.05-0.95 (m, 1H), 0.85 (d, J = 6.7 Hz, 6H) F153 White Foam — 3368, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2958, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2874, [M + H]⁺ 8.48 (d, J = 8.2 Hz, 1H), 172.11, 1742, calcd for 7.98 (d, J = 5.2 Hz, 168.64, 1529 C₂₄H₃₇N₂O₇, 1H), 6.86 (d, J = 5.2 Hz, 155.34, 465.2595; 1H), 4.76 (dq, J = 9.6, 148.71, found, 6.4 Hz, 1H), 140.52, 465.2617 4.58 (ddd, J = 10.8, 8.2, 130.41, 7.3 Hz, 1H), 4.30 (td, 109.45, 84.20, J = 5.3, 2.8 Hz, 1H), 83.37, 81.33, 3.52-3.41 (m, 2H), 73.54, 70.92, 3.36-3.24 (m, 2H), 56.07, 51.33, 2.37 (dtd, J = 13.5, 33.33, 32.92, 7.0, 6.5, 1.9 Hz, 1H), 32.39, 27.79, 2.14 (dddd, J = 15.8, 23.34, 23.26, 10.1, 8.3, 5.3 Hz, 23.22, 18.27, 1H), 1.86-1.46 (m, 18.11, 10.78 12H), 1.42-1.33 (m, 1H), 1.39 (d, J = 6.4 Hz, 3H), 0.93 (t, J = 7.4 Hz, 3H), 0.94-0.88 (m, 1H) F154 White Foam — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2959, (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ 2875, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.27, 1746, calcd for 1H), 6.93 (d, J = 5.4 Hz, 172.73, 1504 C₂₉H₄₅N₂O₉, 1H), 162.93, 565.3120; 5.83-5.69 (m, 2H), 160.25, found, 4.74 (dq, J = 9.7, 6.5 Hz, 145.59, 565.3134 1H), 4.60 (dt, J = 10.8, 144.21, 7.6 Hz, 1H), 142.11, 4.34-4.24 (m, 1H), 109.51, 89.94, 3.89 (s, 3H), 84.28, 83.36, 3.51-3.41 (m, 2H), 81.40, 73.25, 3.36-3.26 (m, 2H), 70.90, 56.13, 2.55 (hept, J = 7.0 Hz, 51.66, 33.86, 1H), 2.37 (dt, J = 14.0, 33.43, 32.93, 6.8 Hz, 1H), 32.39, 27.88, 2.18-2.04 (m, 1H), 23.34, 23.26, 1.85-1.44 (m, 12H), 23.22, 18.68, 1.38 (d, J = 6.4 Hz, 18.34, 18.10, 3H), 1.37-1.25 (m, 10.78 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.93 (t, J = 7.4 Hz, 3H), 0.93-0.88 (m, 1H) F155 White Foam — 3380, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2958 (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) δ 2874, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 172.74, 1746, calcd for 1H), 6.94 (d, J = 5.4 Hz, 170.31, 1678 C₂₇H₄₁N₂O₉, 1H), 5.74 (s, 162.96, 537.2807; 2H), 4.74 (dq, J = 9.6, 160.27, found, 6.4 Hz, 1H), 145.73, 537.2824 4.60 (dt, J = 10.8, 7.6 Hz, 143.99, 1H), 4.30 (h, J = 3.4 Hz, 142.45, 1H), 3.91 (s, 3H), 109.57, 89.57, 3.53-3.41 (m, 2H), 84.28, 83.36, 3.38-3.24 (m, 2H), 81.39, 73.27, 2.38 (ddd, J = 13.7, 70.90, 56.18, 7.0, 5.3 Hz, 1H), 51.66, 33.42, 2.19-2.09 (m, 1H), 32.93, 32.39, 2.07 (s, 3H), 27.87, 23.34, 1.86-1.44 (m, 12H), 1.38 (d, J = 6.4 Hz, 23.26, 23.21, 3H), 20.89, 18.34, 1.36-1.29 (m, 1H), 0.93 (t, 18.10, 10.78 J = 7.4 Hz, 3H), 0.91-0.79 (m, 1H) F156 White Foam — 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2952, (m/z) 12.04 (s, 1H), (CDCl₃) δ 2871, [M + H]⁺ 8.50 (d, J = 8.2 Hz, 1H), 175.77, 1732, calcd for 7.99 (dd, J = 5.2, 1.4 Hz, 171.84, 1530 C₂₇H₃₉N₂O₈, 1H), 6.87 (d, J = 5.2 Hz, 168.67, 519.2701; 1H), 155.33, found, 4.94-4.81 (m, 2H), 148.69, 519.2719 4.61 (dt, J = 10.9, 7.6 Hz, 140.57, 1H), 4.15-4.07 (m, 130.34, 1H), 3.58 (dd, J = 9.5, 109.49, 83.35, 7.4 Hz, 1H), 80.01, 77.66, 2.74 (p, J = 8.1 Hz, 1H), 73.39, 56.08, 2.36 (dt, J = 13.8, 7.0 Hz, 51.27, 44.07, 1H), 33.12, 32.91, 2.22-2.07 (m, 1H), 1.94 (m, 32.35, 30.55, 1H), 1.86 (q, J = 7.2 Hz, 29.51, 29.31, 2H), 25.82, 25.77, 1.81-1.46 (m, 15H), 23.13, 23.11, 1.46-1.32 (m, 1H), 1.43 (d, J = 6.4 Hz, 18.41, 18.00 3H), 1.10 (dd, J = 16.2, 7.2 Hz, 1H) F157 white foam — 3380, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2948, (m/z) 8.40 (d, J = 8.1 Hz, (CDCl₃) δ 2872, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.25, 1744, calcd for 1H), 6.94 (d, J = 5.4 Hz, 175.79, 1678 C₃₂H₄₇N₂O₁₀, 1H), 172.44, 619.3225; 5.83-5.70 (m, 2H), 162.96, found, 4.89-4.82 (m, 2H), 160.24, 619.3256 4.62 (dt, J = 10.8, 7.6 Hz, 145.63, 1H), 4.17-4.03 (m, 144.15, J = 4.1 Hz, 1H), 142.01, 3.89 (s, 3H), 3.58 (dd, J = 9.5, 109.56, 89.87, 7.3 Hz, 1H), 83.33, 80.07, 2.80-2.66 (m, 1H), 77.81, 73.10, 2.54 (hept, J = 7.0 Hz, 56.14, 51.60, 1H), 2.36 (dt, J = 13.8, 44.09, 33.86, 6.8 Hz, 1H), 33.21, 32.91, 2.19-2.05 (m, 1H), 32.36, 30.55, 2.01-1.89 (m, 1H), 29.51, 29.33, 1.86 (td, J = 7.9, 7.5, 25.82, 25.77, 5.8 Hz, 2H), 23.13, 23.11, 1.79-1.46 (m, 14H), 18.68, 18.46, 1.41 (d, J = 6.4 Hz, 3H), 17.99 1.39-1.26 (m, 2H), 1.14 (d, J = 7.0 Hz, 6H), 1.13-1.01 (m, 1H) F158 white foam — 3360, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2951, (m/z) 8.34 (d, J = 8.1 Hz, (CDCl₃) δ 2871, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 175.80, 1732, calcd for 1H), 6.95 (d, J = 5.4 Hz, 172.45, 1677 C₃₀H₄₃N₂O₁₀, 1H), 5.74 (s, 170.29, 591.2912; 2H), 4.89-4.82 (m, 162.99, found, 2H), 4.62 (dt, J = 10.8, 160.25, 591.2941 7.7 Hz, 1H), 145.76, 4.10 (p, J = 4.6 Hz, 143.94, 1H), 3.91 (s, 3H), 142.34, 3.58 (dd, J = 9.5, 7.3 Hz, 109.62, 89.51, 1H), 83.33, 80.07, 2.79-2.67 (m, 1H), 77.79, 73.12, 2.42-2.29 (m, 1H), 56.19, 51.61, 2.19-2.08 (m, 1H), 2.07 (s, 3H), 44.09, 33.19, 1.99-1.89 (m, 1H), 32.91, 32.36, 1.86 (td, J = 8.0, 7.5, 30.55, 29.51, 5.7 Hz, 2H), 29.35, 25.82, 1.80-1.46 (m, 15H), 25.77, 23.13, 1.41 (d, J = 6.4 Hz, 3H), 23.11, 20.89, 1.34 (q, J = 11.5 Hz, 18.46, 17.99 1H), 1.09 (ddt, J = 16.0, 7.2, 2.4 Hz, 1H) F159 white foam — 3350, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2951, (m/z) 8.55 (d, J = 8.1 Hz, (CDCl₃) δ 2871, [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 175.79, 1731, calcd for 1H), 7.00 (d, J = 5.4 Hz, 172.32, 1676 C₂₉H₄₁N₂O₉, 1H), 168.90, 561.2807; 4.92-4.77 (m, 2H), 162.42, found, 4.61 (ddd, J = 10.8, 8.4, 159.41, 561.2834 7.1 Hz, 1H), 146.72, 4.14-4.01 (m, 1H), 3.91 (s, 141.33, 3H), 3.56 (dd, J = 9.5, 137.47, 7.3 Hz, 1H), 109.82, 83.32, 2.79-2.65 (m, 1H), 80.07, 77.74, 2.40 (s, 3H), 73.12, 56.29, 2.38-2.25 (m, 1H), 2.11 (ddt, J = 16.3, 51.34, 44.08, 10.0, 7.4 Hz 33.39, 32.92, 1H), 2.00-1.89 (m, 32.35, 30.55, 1H), 1.85 (td, J = 7.5, 29.51, 29.39, 5.6 Hz, 2H), 25.82, 25.76, 1.79-1.45 (m, 15H), 23.13, 23.11, 1.40 (d, J = 6.4 Hz, 3H), 20.75, 18.43, 1.37-1.26 (m, 1H), 17.97 1.15-1.02 (m, 1H) F160 White Foam — 3370, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2952, (m/z) 12.05 (d, J = 0.6 Hz, (CDCl₃) δ 1743, [M + H]⁺ 1H), 8.46 (d, J = 8.1 Hz, 172.00, 1503 calcd for 1H), 7.99 (d, J = 5.2 Hz, 168.68, C₂₇H₃₄FN₂O₇, 1H), 155.36, 517.2345; 7.02-6.92 (m, 2H), 148.73, found, 6.92-6.76 (m, 3H), 140.55, 517.2364 4.87 (dq, J = 9.7, 6.4 Hz, 130.34, 1H), 4.63 (dt, J = 10.8, 117.87, 7.7 Hz, 1H), 117.79, 4.31-4.17 (m, 2H), 116.02, 3.94 (s, 3H), 115.79, 3.72 (dd, J = 9.6, 7.1 Hz, 109.49, 83.97, 1H), 2.37 (dt, J = 13.7, 83.86, 80.93, 6.9 Hz, 1H), 73.28, 56.09, 2.14-2.09 (m, 1H), 51.24, 33.21, 1.89-1.76 (m, 1H), 32.85, 32.47, 1.76-1.50 (m, 9H), 28.07, 23.13, 1.46 (d, J = 6.4 Hz, 23.11, 18.21, 3H), 1.41-1.27 (m, 18.06 1H), 1.09-0.97 (m, 1H) F161 White Foam — 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2946, (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ 1746, [M + H]⁺ 1H), 8.26 (d, J = 5.3 Hz, 176.27, 1503 calcd for 1H), 172.61, C₃₂H₄₂FN₂O₉, 7.03-6.91 (m, 3H), 162.97, 617.2869; 6.91-6.81 (m, 2H), 160.25, found, 5.88-5.65 (m, 2H), 4.85 (dq, J = 9.6, 156.31, 617.2887 6.4 Hz, 1H), 153.74, 4.64 (dt, J = 10.8, 7.6 Hz, 153.72, 1H), 4.31-4.18 (m, 145.60, 2H), 3.71 (dd, J = 9.6, 144.22, 7.1 Hz, 1H), 142.00, 2.55 (hept, J = 7.0 Hz, 117.87, 1H), 2.44-2.29 (m, 117.79, 1H), 2.18-2.01 (m, 115.99, 1H), 1.87-1.49 (m, 115.76, 10H), 1.45 (d, J = 6.4 Hz, 109.56, 89.89, 3H), 84.05, 83.84, 1.36-1.25 (m, 1H), 1.14 (d, J = 7.0 Hz, 81.00, 72.98, 6H), 1.02 (dd, 56.14, 51.58, J = 16.0, 7.6 Hz, 1H) 33.86, 33.29, 32.85, 32.47, 28.15, 23.12, 23.11, 18.68, 18.28, 18.05 F162 White Foam — 3375, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2952, (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ 1749, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.62, 1503 calcd for 1H), 170.31, C₃₀H₃₈FN₂O₉, 7.04-6.92 (m, 3H), 162.99, 589.2556; 6.92-6.82 (m, 2H), 5.74 (s, 2H), 160.27, found, 4.85 (dq, J = 9.7, 6.4 Hz, 156.31, 589.2572 1H), 4.64 (dt, J = 10.8, 153.73, 7.6 Hz, 1H), 153.71, 4.32-4.18 (m, 2H), 145.74, 3.91 (s, 3H), 144.00, 3.71 (dd, J = 9.6, 7.1 Hz, 142.34, 1H), 2.44-2.30 (m, 117.88, 1H), ), 117.80, 2.15-2.05 (m, 1H), 2.07 (s, 3H), 115.99, 1.87-1.47 (m, 10H), 115.76, 1.45 (d, J = 6.4 Hz, 109.62, 89.52, 3H), 1.36-1.26 (m, 84.05, 83.84, 1H), 1.06-0.95 (m, 80.99, 73.00, 1H) 56.19, 51.58, 33.28, 32.85, 32.47, 28.15, 23.12, 23.11, 20.89, 18.28, 18.05 F163 Colorless — 3365, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2939, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2869, [M + H]⁺ 8.48 (d, J = 8.1 Hz, 1H), 172.07, 1742, calcd for 7.98 (d, J = 5.2 Hz, 168.65, 1649, C₃₀H₄₁N₂O₇, 1H), 7.33-7.23 (m, 155.35, 1576, 541.2908; 2H), 7.19 (d, J = 7.3 Hz, 148.73, 1527, found, 3H), 6.86 (d, J = 5.2 Hz, 141.98, 1450 541.2915 1H), 4.81 (dq, 140.51, J = 9.5, 6.4 Hz, 1H), 130.38, 4.58 (dt, J = 10.7, 7.6 Hz, 128.34, 1H), 3.99 (dq, J = 7.6, 128.32, 3.3, 2.4 Hz, 1H), 125.80, 3.93 (s, 3H), 3.85 (dt, 109.47, 83.89, J = 8.9, 6.5 Hz, 1H), 81.67, 79.14, 3.63 (dt, J = 8.9, 6.7 Hz, 73.55, 73.37, 1H), 3.43 (ddd, J = 7.1, 56.07, 51.32, 5.2, 1.7 Hz, 33.53, 33.38, 1H), 3.33 (dd, J = 9.5, 32.55, 32.04, 7.3 Hz, 1H), 31.88, 28.35, 2.78-2.59 (m, 2H), 23.64, 23.36, 2.36 (dtd, J = 13.6, 7.1, 18.49, 17.96 6.4, 1.9 Hz, 1H), 2.09 (dddd, J = 15.8, 9.9, 8.3, 5.1 Hz, 1H), 2.02-1.80 (m, 2H), 1.77-1.45 (m, 10H), 1.41 (d, J = 6.3 Hz, 3H), 1.40-1.32 (m, 1H), 0.94-0.87 (m, 1H) F164 Colorless — 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2735, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2871, [M + H]⁺ 8.47 (d, J = 8.0 Hz, 1H), 172.07, 1746, calcd for 7.99 (d, J = 5.2 Hz, 168.64, 155.3, 1650, C₂₆H₄₁N₂O₇, 1H), 6.86 (d, J = 5.2 Hz, 148.70, 1522, 493.2908; 1H), 4.79 (dqd, J = 9.0, 140.50, 1487 found, 6.4, 3.3 Hz, 130.39, 493.2921 1H), 4.58 (dt, J = 10.7, 109.45, 83.77, 7.4 Hz, 1H), 81.66, 79.19, 4.01 (dq, J = 6.4, 2.2 Hz, 74.32, 73.45, 1H), 3.94 (s, 3H), 56.06, 51.30, 3.81 (dt, J = 8.8, 6.6 Hz, 33.53, 33.40, 1H), 33.35, 31.91, 3.68-3.54 (m, 1H), 30.07, 28.37, 3.48-3.38 (m, 1H), 23.66, 23.36, 3.38-3.27 (m, 1H), 2.37 (dtd, J = 13.8, 22.60, 18.47, 7.2, 6.6, 2.0 Hz, 17.85, 14.04 1H), 2.09 (dddd, J = 15.7, 10.1, 8.4, 5.1 Hz, 1H), 1.80-1.46 (m, 11H), 1.40 (d, J = 6.4 Hz, 3H), 1.37-1.29 (m, 4H), 0.96-0.81 (m, 6H) F165 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2941, (m/z) 8.31 (d, J = 8.1 Hz, (CDCl₃) δ 2868, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.69, 1744, calcd for 1H), 170.28, 1676, C₃₃H₄₅N₂O₉, 7.33-7.24 (m, 2H), 7.19 (d, J = 7.3 Hz, 162.97, 1499 613.3120; 3H), 6.94 (d, 160.27, found, J = 5.4 Hz, 1H), 145.74, 613.3119 5.74 (s, 2H), 4.79 (dq, J = 9.6, 143.98, 6.4 Hz, 1H), 142.41, 4.60 (dt, J = 10.7, 7.5 Hz, 142.00, 1H), 3.99 (dq, J = 5.7, 128.34, 3.6 Hz, 1H), 128.32, 3.90 (s, 3H), 3.85 (dt, J = 9.0, 125.79, 6.4 Hz, 1H), 109.61, 89.54, 3.63 (dt, J = 8.8, 6.7 Hz, 83.93, 81.75, 1H), 3.42 (ddd, J = 7.2, 79.11, 73.53, 5.2, 1.7 Hz, 1H), 73.09, 56.19, 3.32 (dd, J = 9.6, 7.3 Hz, 51.64, 33.51, 1H), 33.47, 32.55, 2.77-2.59 (m, 2H), 32.04, 31.88, 2.43-2.31 (m, 1H), 28.42, 23.63, 2.14-2.07 (m, 1H), 2.07 (s, 3H) 23.35, 20.88, 1.98-1.80 (m, 3H), 18.55, 17.95 1.77-1.43 (m, 9H), 1.40 (d, J = 6.4 Hz, 3H), 1.37-1.27 (m, 1H), 0.94-0.83 (m, 1H) F166 Colorless — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2974, (m/z) 8.31 (d, J = 7.9 Hz, (CDCl₃) δ 2934, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.69, 1744, calcd for 1H), 6.95 (d J = 5.4 Hz, 170.27, 1677, C₂₉H₄₅N₂O₉, 1H), 5.74 (s, 162.96, 1502, 565.3120; 2H), 4.77 (dqd, J = 9.9, 160.26, 1455 found, 6.4, 3.7 Hz, 1H), 145.72, 565.3120 4.60 (dt, J = 10.6, 7.6 Hz, 143.97, 1H), 4.01 (dtd, J = 7.4, 142.43, 3.7, 1.5 Hz, 109.58, 89.55, 1H), 3.91 (s, 3H), 83.82, 81.75, 3.80 (dt, J = 8.8, 6.6 Hz, 79.15, 74.29, 1H), 3.58 (dt, J = 8.7, 73.17, 56.18, 6.8 Hz, 1H), 51.63, 33.52, 3.45-3.38 (m, 1H), 33.49, 31.91, 3.31 (dd, J = 9.6, 7.4 Hz, 30.08, 28.44, 1H), 2.43-2.31 (m, 28.37, 23.65, 1H), 2.14-2.01 (m, 23.36, 22.59, 1H), 2.07 (s, 3H), 20.87, 18.53, 1.81-1.46 (m, 11H), 17.84, 14.03 1.38 (d, J = 6.2 Hz, 3H), 1.33 (dtt, J = 10.5, 4.2, 2.3 Hz, 5H), 0.93-0.84 (m, 5H) F167 White Foam — 3366, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2950, (m/z) 12.07 (d, J = 0.7 Hz, (CDCl₃) δ 1742, [M + H]⁺ 1H), 8.46 (d, J = 8.2 Hz, 172.02, 1505 calcd for 1H), 7.98 (d, J = 5.2 Hz, 168.67, C₂₈H₃₇N₂O₈, 1H), 155.35, 529.2544; 6.96-6.64 (m, 5H), 154.32, found, 4.86 (dq, J = 9.7, 6.4 Hz, 151.48, 529.2544 1H), 4.62 (dt, J = 10.8, 148.72, 7.7 Hz, 1H), 140.53, 4.30 (tt, J = 5.5, 3.6 Hz, 130.36, 1H), 4.19 (ddd, J = 7.1, 118.14, 5.2, 1.7 Hz, 114.63, 1H), 3.94 (s, 3H), 109.48, 84.40, 3.77 (s, 3H), 83.80, 80.93, 3.72 (dd, J = 9.6, 7.1 Hz, 73.32, 56.08, 1H), 2.37 (dt, J = 13.7, 55.66, 51.25, 7.0 Hz, 1H), 33.26, 32.93, 2.17-2.08 (m, 1H), 32.47, 27.91, 1.90-1.48 (m, 10H), 23.15, 18.23, 1.46 (d, J = 6.5 Hz, 18.09 3H), 1.33 (dt, J = 13.5, 11.4 Hz, 1H), 1.03-0.92 (m, 1H) F168 White Foam — 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2946, (m/z) 12.07 (d, J = 0.7 Hz, (CDCl₃) δ 1742, [M + H]⁺ 1H), 8.47 (d, J = 8.1 Hz, 172.05, 1528 calcd for 1H), 7.99 (d, J = 5.2 Hz, 168.66, C₂₅H₃₆F₃N₂O₇, 1H), 6.87 (d, 155.35, 533.2469; J = 5.2 Hz, 1H), 148.72, found, 4.76 (dq, J = 9.5, 6.4 Hz, 140.53, 533.2472 1H), 4.64-4.53 (m, 130.38, 1H), 4.24 (td, J = 5.3, 128.62, 2.9 Hz, 1H), 125.87, 3.61-3.52 (m, 1H), 109.47, 84.27, 3.47-3.39 (m, 2H), 83.46, 81.20, 3.35-3.31 (m, 1H), 73.50, 67.14, 2.38 (dt, J = 13.7, 6.8 Hz, 56.08, 51.28, 1H), 2.31-2.03 (m, 33.25, 32.85, 3H), 1.89-1.78 (m, 32.40, 31.29, 2H), 1.75-1.52 (m, 31.00, 30.71, 10H), 1.41-1.33 (m, 30.43, 27.72, 1H), 1.40 (d, J = 6.4 Hz, 23.23, 23.20, 3H), 0.94 (ddt, J = 16.2, 22.88, 22.86, 7.6, 1.9 Hz, 22.83, 22.80, 1H) 18.21, 18.05 F169 White Foam — 3378, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2947, (m/z) 8.36 (d, J = 8.0 Hz, (CDCl₃) δ 1745, [M + H]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.27, 1504 calcd for 1H), 6.93 (d, J = 5.4 Hz, 172.63, C₃₃H₄₅N₂O₁₀, 1H), 162.96, 629.3069; 6.91-6.85 (m, 2H), 160.25, found, 6.85-6.77 (m, 2H), 154.27, 629.3075 4.84 (dq, J = 9.6, 6.4 Hz, 151.54, 1H), 4.64 (dt, J = 10.8, 145.60, 7.6 Hz, 1H), 144.21, 4.30 (tt, J = 5.5, 3.7 Hz, 142.03, 1H), 4.18 (ddd, J = 7.1, 118.15, 5.2, 1.7 Hz, 114.61, 1H), 3.89 (s, 3H), 109.54, 89.90, 3.77 (s, 3H), 84.49, 83.78, 3.71 (dd, J = 9.6, 7.1 Hz, 81.00, 73.02, 1H), 2.55 (hept, J = 7.0 Hz, 56.13, 55.66, 1H), 2.37 (dt, 51.58, 33.86, J = 13.7, 7.0 Hz, 1H), 33.35, 32.93, 2.17-2.06 (m, 1H), 32.47, 27.99, 1.87-1.47 (m, 10H), 23.14, 18.68, 1.44 (d, J = 6.4 Hz, 18.30, 18.08 3H), 1.35-1.23 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 1.03-0.89 (m, 1H) F170 White Foam — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2949, (m/z) 8.31 (d, J = 8.1 Hz, (CDCl₃) δ 1748, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 172.64, 1677, calcd for 1H), 6.94 (d, J = 5.4 Hz, 170.31, 1504 C₃₁H₄₁N₂O₁₀, 1H), 162.98, 601.2756; 6.92-6.85 (m, 2H), 160.26, found, 6.85-6.77 (m, 2H), 5.74 (s, 154.28, 601.2763 2H), 4.84 (dq, J = 9.6, 151.54, 6.4 Hz, 1H), 145.73, 4.64 (dt, J = 10.8, 7.6 Hz, 144.00, 1H), 4.30 (tt, J = 5.5, 142.37, 3.7 Hz, 1H), 118.15, 4.18 (ddd, J = 7.0, 5.2, 1.7 Hz, 114.61, 1H), 3.91 (s, 3H), 109.60, 89.54, 3.77 (s, 3H), 84.49, 83.79, 3.71 (dd, J = 9.6, 7.1 Hz, 80.99, 73.04, 1H), 2.37 (dt, J = 13.6, 56.19, 55.66, 7.0 Hz, 1H), 51.59, 33.35, 2.12 (ddd, J = 10.7, 32.93, 32.47, 8.2, 5.4 Hz, 1H), 27.99, 23.14, 2.07 (s, 3H), 20.89, 18.30, 1.89-1.47 (m, 10H), 1.44 (d, J = 6.4 Hz, 18.08 3H), 1.35-1.21 (m, 1H), 0.97 (dd, J = 16.1, 7.8 Hz, 1H) F171 Colorless — 3380, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2946, (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ 2876, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.27, 1745, calcd for 1H), 6.93 (d, J = 5.4 Hz, 172.66, 1676 C₃₀H₄₄F₃N₂O₉, 1H), 162.95, 633.2993; 5.81-5.71 (m, 2H), 160.24, found, 4.74 (dq, J = 9.5, 6.4 Hz, 145.60, 633.3010 1H), 4.60 (dt, J = 10.8, 144.21, 7.5 Hz, 1H), 142.06, 4.28-4.20 (m, 1H), 128.63, 3.89 (s, 3H), 125.89, 3.60-3.51 (m, 1H), 109.54, 89.90, 3.46-3.38 (m, 2H), 84.34, 83.43, 3.32 (ddd, J = 7.1, 5.3, 1.6 Hz, 81.26, 73.21, 1H), 2.55 (hept, J = 7.0 Hz, 67.13, 56.14, 1H), 51.62, 33.86, 2.38 (dt, J = 13.7, 6.8 Hz, 33.34, 32.86, 1H), 2.30-2.01 (m, 32.40, 31.01, 3H), 1.92-1.48 (m, 30.73, 27.81, 12H), 1.39 (d, J = 6.4 Hz, 23.23, 23.20, 3H), 22.86, 22.83, 1.36-1.30 (m, 1H), 1.14 (d, J = 7.0 Hz, 18.68, 18.28, 6H), 18.04 0.94 (ddt, J = 16.2, 7.7, 2.1 Hz, 1H) F172 Colorless — 3381, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2949, (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) δ 2874, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 172.67, 1747, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.31, 1677 C₂₈H₄₀F₃N₂O₉, 1H), 5.74 (s, 162.98, 605.2680; 2H), 4.74 (dq, J = 9.5, 160.26, found, 6.4 Hz, 1H), 145.74, 605.2686 4.66-4.54 (m, 1H), 143.99, 4.24 (td, J = 5.2, 3.4 Hz, 142.40, 1H), 3.91 (s, 3H), 128.63, 3.61-3.51 (m, 1H), 125.89, 3.47-3.39 (m, 2H), 109.60, 89.54, 3.32 (ddd, J = 7.1, 84.33, 83.44, 5.4, 1.7 Hz, 1H), 81.26, 73.23, 2.38 (dt, J = 13.7, 6.9 Hz, 67.13, 56.19, 1H), 2.31-2.08 (m, 51.62, 33.33, 3H), 2.07 (s, 3H), 32.86, 32.40, 1.92-1.46 (m, 12H), 31.30, 31.01, 1.39 (d, J = 6.4 Hz, 30.73, 30.44, 3H), 1.33 (dt, J = 11.0, 27.81, 23.23, 1.8 Hz, 1H), 23.20, 22.89, 0.93 (ddt, J = 16.1, 22.86, 22.83, 7.6, 1.8 Hz, 1H) 22.80, 20.89, 18.28, 18.04 F173 Colorless — 3379, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2949, (m/z) 8.53 (d, J = 8.4 Hz, (CDCl₃) δ 1772, [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 172.55, 1743, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.92, 1678 C₂₇H₃₈F₃N₂O₈, 1H), 4.73 (dq, 162.40, 575.2575; J = 9.6, 6.4 Hz, 1H), 159.43, found, 4.59 (ddd, J = 10.8, 146.70, 575.2588 8.4, 7.2 Hz, 1H), 141.40, 4.26-4.22 (m, 1H), 137.49, 3.91 (s, 3H), 128.62, 3.61-3.50 (m, 1H), 125.88, 3.45-3.39 (m, 2H), 3.32 (ddd, J = 7.1, 109.80, 84.33, 5.3, 1.6 Hz, 83.43, 81.26, 1H), 2.40 (s, 3H), 73.24, 67.14, 2.41-2.33 (m, 1H), 56.29, 51.35, 2.30-2.02 (m, 3H), 33.53, 32.87, 1.91-1.47 (m, 12H), 32.40, 31.30, 1.37 (d, J = 6.4 Hz, 31.01, 30.72, 3H), 1.36-1.27 (m, 30.44, 27.84, 1H), 0.93 (ddt, J = 16.0, 23.23, 23.19, 7.5, 2.0 Hz, 1H) 22.88, 22.85, 22.82, 22.79, 20.75, 18.23, 18.02 F174 Off-White — — ESIMS — — Solid m/z 328.3 ([M + H]⁺⁾ F175 White Solid — 2959, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2936, (m/z) 8.69 (br s, 3H), (CDCl₃) δ 2878, [M + H]⁺ 4.74 (t, J = 7.2 Hz, 1H), 169.99, 83.91, 1751, calcd for 4.01-3.97 (m, 1H), 83.53, 75.52, 1207 C₁₅H₃₀NO₄, 3.75 (dt, J = 8.9, 6.5 Hz, 74.21, 70.90, 288.2169; 1H), 3.51 (ddt, J = 29.8, 52.10, 31.28, found, 9.0, 6.6 Hz, 27.87, 23.49, 288.2167 2H), 3.35-3.15 (m, 23.33, 17.81, 3H), 2.56-2.45 (m, 17.77, 10.76, 1H), 2.11 (s, 1H), 10.67 1.75-1.47 (m, 7H), 1.39 (d, J = 6.2 Hz, 3H), 0.92 (td, J = 7.4, 1.8 Hz, 6H), 0.86-0.71 (m, 1H) F176 White Solid 226-229 2958, HRMS-ESI ¹H NMR (400 MHz, ¹³ C NMR (101 MHz, 2873, (m/z) (CD₃OD) δ 4.78 (pd, J = 6.3, (CD₃OD) δ 2110, [M + Na]⁺ 2.1 Hz, 1H), 169.68, 83.82, 1743, calcd for 3.93 (dd, J = 10.7, 83.37, 75.79, 1455, C₁₆H₃₁NNaO₄, 7.4 Hz, 1H), 3.78 (dt, 75.26, 74.00, 1226 324.2145; J = 8.9, 6.5 Hz, 1H), 51.45, 30.62, found, 3.58 (dt, J = 8.8, 6.6 Hz, 28.75, 27.26, 324.2156 1H), 23.24, 18.86, 3.38-3.33 (m, 3H), 3.15 (dd, J = 8.7, 18.80, 17.50, 6.2 Hz, 1H), 17.17, 10.02 2.33-2.13 (m, 2H), 1.81 (dp, J = 13.3, 6.7 Hz, 1H), 1.68 (tt, J = 9.8, 4.7 Hz, 2H), 1.62-1.52 (m, 2H), 1.51-1.42 (m, 1H), 1.41 (d, J = 6.3 Hz, 3H), 0.98-0.86 (m, 9H), 0.84 (dt, J = 16.9, 5.0 Hz, 1H) F177 White — 3349, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³ C NMR Foamy Solid 1635, (m/z) 8.70 (bs, 3H), (CDCl₃) δ 1502, [M + H]⁺ 6.99-6.82 (m, 6H), 170.06, 1203 calcd for 6.79-6.68 (m, 2H), 157.87 (d, J = 240.2 Hz), C₂₁H₂₃F₂NO₄, 5.10-4.97 (m, 1H), 155.46 (d, J = 2.0 Hz), 392.1668; 4.48-4.40 (m, 1H), 154.48 (d, J = 199.0 Hz), found, 4.39-4.32 (m, 1H), 153.49 (d, J = 2.0 Hz), 392.1664 4.26-4.09 (m, 1H), 118.13 (d, J = 8.0 Hz), 2.67-2.47 (m, 1H), 117.72 (d, J = 8.1 Hz), 2.29-2.11 (m, 1H), 116.14 (d, J = 4.9 Hz), 1.92-1.66 (m, 3H), 1.37 (d, 115.92 (d, J = 4.6 Hz), J = 5.9 Hz, 3H), 83.27, 83.09, 1.18-1.04 (m, 1H) 73.33, 52.43, 30.95, 28.65, 18.17, 18.06 F178 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹ F NMR m/z 354.2 8.71 (bs, 3H), (CDCl₃) δ −122.97 ([M + H]⁺) 7.04-6.87 (m, 4H), 5.01-4.89 (m, 1H), 4.25 (dd, J = 9.5, 7.2 Hz, 1H), 4.16-4.03 (m, 1H), 3.54-3.46 (m, 1H), 3.22 (dd, J = 8.7, 6.5 Hz, 1H), 3.02 (dd, J = 8.7, 6.1 Hz, 1H), 2.63-2.51 (m, 1H), 2.29-2.10 (m, 1H), 1.89-1.72 (m, 1H), 1.74-1.59 (m, 3H), 1.33 (d, J = 6.3 Hz, 3H), 1.02-0.90 (m, 1H), 0.79 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 6.7 Hz, 3H) F179 White Solid — — ESIMS ¹H NMR (CDCl₃) ¹⁹ F NMR m/z 354.2 δ 8.64 (bs, 3H), (CDCl₃) δ −122.79 ([M + H]⁺) 7.30-7.23 (m, 1H), 7.22-7.13 (m, 1H), 6.98-6.90 (m, 1H), 6.87-6.80 (m, 1H), 4.87-4.76 (m, 1H), 4.27-4.17 (m, 1H), 4.16-4.01 (m, 1H), 3.57-3.47 (m, 2H), 3.36 (dd, J = 8.7, 6.5 Hz, 1H), 2.89 (t, J = 7.6 Hz, 1H), 2.71 (t, J = 7.6 Hz, 1H), 2.59-2.39 (m, 1H), 2.18-1.99 (m, 1H), 1.80-1.56 (m, 3H), 1.42 (d, J = 6.0 Hz, 3H), 0.83 (d, J = 6.6 Hz, 3H), 0.79 (d, J = 6.7 Hz, 3H) F180 White Solid 236-240 2957, HRMS-ESI ¹H NMR (CD₃OD) δ ¹³ C NMR 2878, (m/z) 6.50 (dtd, J = 15.7, (CD₃OD) δ 1742, [M + Na]⁺ 4.0, 2.0 Hz, 1H), 170.03, 1458, calcd for 5.98 (dqt, J = 15.5, 6.6, 137.51, 1108 C₁₇H₂₈F₃NNaO₄, 2.1 Hz, 1H), 117.43, 390.1863; 4.48 (ddt, J = 15.7, 6.6, 117.09, 83.80, found, 3.2 Hz, 1H), 83.59, 75.48, 390.1874 4.41-4.29 (m, 1H), 73.41, 70.70, 3.93 (dd, J = 10.7, 7.4 Hz, 51.45, 30.77, 1H), 3.55-3.40 (m, 28.68, 27.05, 2H), 3.37-3.32 (m, 18.45, 18.34, 2H), 3.14 (dd, J = 8.7, 17.37, 16.72; 6.0 Hz, 1H), ¹⁹ F NMR 2.24 (dtd, J = 18.3, 9.1, (CD₃OD) δ 4.6 Hz, 2H), 1.80 (dp, −65.82 (dt, J = 8.4, J = 13.2, 6.7 Hz, 1H), 2.5 Hz) 1.69 (tt, J = 9.8, 4.5 Hz, 2H), 1.57-1.44 (m, 1H), 1.42 (d, J = 6.4 Hz, 3H), 0.91 (dd, J = 6.7, 4.4 Hz, 6H), 0.86 (t, J = 4.7 Hz, 1H) F181 White Solid — 2933, HRMS-ESI ¹H NMR (CD₃OD) δ ¹³ C NMR 2859, (m/z) 4.78 (pd, J = 6.3, 2.0 Hz, (CD₃OD) δ 1743, [M + H]⁺ 1H), 3.93 (dd, J = 10.8, 169.83, 83.87, 1456 calcd for 7.4 Hz, 1H), 83.43, 75.59, C₁₈H₃₆NO₄, 3.80 (dt, J = 8.9, 6.5 Hz, 73.84, 73.39, 330.2639; 1H), 3.62 (dt, J = 8.9, 51.40, 30.57, found, 6.6 Hz, 1H), 29.73, 28.75, 330.2643 3.39-3.32 (m, 2H), 28.19, 27.18, 3.15 (dd, J = 8.7, 6.1 Hz, 22.19, 18.50, 1H), 2.31-2.14 (m 18.43, 17.41, 2H), 1.81 (dp, J = 13.2, 16.77, 12.98 6.6 Hz, 1H), 1.68 (tt, J = 9.8, 4.6 Hz, 2H), 1.62-1.49 (m, 2H), 1.48-1.38 (m, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.40-1.28 (m, 4H), 0.97-0.86 (m, 9H), 0.87-0.79 (m, 1H) F182 Colorless — — ESIMS ¹H NMR (CDCl₃) ¹³ C NMR Solid m/z 416.3 δ 8.65 (bs, 3H), (CDCl₃) δ ([M + H]⁺) 7.04-6.92 (m, 2H), 170.03, 6.83-6.66 (m, 6H), 154.57, 5.11-4.92 (m, 1H), 154.46, 4.46-4.36 (m, 1H), 153.68, 4.36-4.25 (m, 1H), 151.51, 4.23-4.07 (m, 1H), 118.44, 3.73 (s, 3H), 3.71 (s, 3H), 117.74, 2.68-2.47 (m, 1H), 114.59, 2.31-2.11 (m, 1H), 114.52, 83.69, 1.90-1.65 (m, 3H), 83.42, 73.48, 1.38 (d, J = 6.2 Hz, 55.61, 52.33, 3H), 1.13-0.95 (m, 30.93, 28.23, 1H) 18.17, 17.94 F183 White Solid 198-200 — — ¹H NMR (CDCl₃)δ ¹³ C NMR 8.64 (bs, 3H), (CDCl₃) δ 6.92-6.71 (m, 4H), 170.03, 4.90-4.72 (m, 1H), 154.32, 4.24-4.15 (m, 1H), 151.36, 4.15-4.02 (m, 1H), 3.76 (s, 118.02, 3H), 3.62-3.49 (m, 114.64, 84.25, 2H), 3.37 (dd, J = 8.7, 83.13, 80.78, 6.6 Hz, 1H), 73.79, 55.65, 2.57-2.41 (m, 1H), 52.21, 30.86, 2.20-2.02 (m, 1H), 29.03, 28.04, 1.84-1.54 (m, 4H), 19.43, 19.33, 1.43 (d, J = 6.2 Hz, 3H), 17.89, 17.78 0.96-0.85 (m, 1H), 0.85 (d, J = 6.7 Hz, 3H), 0.82 (d, J = 6.7 Hz, 3H) F184 White Solid 246-248 3432, HRMS-ESI ¹H NMR (CDCl₃) ¹³ C NMR 2957, (m/z) δ 8.68 (bs, 3H), (CDCl₃) δ 1750 [M + H]⁺ 4.67 (dq, J = 11.2, 5.1, 3.8 Hz, 170.18, 83.36, calcd for 1H), 81.60, 80.77, C₁₉H₃₃NO₄, 4.35-4.26 (m, 1H), 78.96, 74.53, 340.2482; 4.06-3.93 (m, 2H), 52.20, 33.54, found, 3.41-3.30 (m, 2H), 32.75, 32.43, 340.2485 2.60-2.42 (m, 1H), 31.70, 31.07, 2.18-2.00 (m, 1H), 28.20, 23.72, 1.86-1.43 (m, 19H), 1.37 (d, J = 6.3 Hz, 23.40, 23.32, 3H), 23.29, 18.06, 0.89-0.74 (m, 1H) 18.01 F185 White Solid 195-197 3389, HRMS-ESI ¹H NMR (CDCl₃)δ ¹³ C NMR 2925, (m/z) 8.73 (bs, 3H), (CDCl₃) δ 1749, [M + H]⁺ 7.31-7.21 (m, 2H), 170.07, 1588, calcd for 7.06-6.99 (m, 2H), 159.61, 1492, C₂₀H₂₉NO₄, 6.98-6.91 (m, 1H), 129.30, 1223 348.2169; 5.04-4.90 (m, 1H), 121.29, found, 4.33 (dd, J = 9.5, 7.3 Hz, 116.19, 82.30, 348.2181 1H), 4.14-4.01 (m, 80.25, 79.73, 1H), 3.95-3.89 (m, 73.83, 52.21, 1H), 3.62-3.55 (m, 33.35, 31.72, 1H), 2.64-2.46 (m, 31.13, 28.43, 1H), 2.26-2.09 (m, 23.38, 22.94, 1H), 2.08-1.37 (m, 18.08, 18.03 11H), 1.33 (d, J = 6.3 Hz, 3H), 1.03-0.89 (m, 1H) F186 White Solid 243-245 3367, HRMS-ESI ¹H NMR (CDCl₃)δ — 2954, (m/z) 8.64 (bs, 3H), 1750, [M + H]⁺ 7.29-7.21 (m, 2H), 1597, calcd for 6.97-6.85 (m, 3H), 1493, C₂₀H₂₉NO₄, 4.87-4.73 (m, 1H), 1236 348.2169; 4.33-4.26 (m, 1H), found, 4.26-4.19 (m, 1H), 348.2137 4.12-3.98 (m, 1H), 3.73-3.61 (m, 2H), 2.58-2.41 (m, 1H), 2.23-2.04 (m, 1H), 1.90-1.45 (m, 10H), 1.42 (d, J = 6.4 Hz, 3H), 0.92 (dd, J = 15.8, 7.2 Hz, 1H) F187 White Solid — 2945, HRMS-ESI ¹H NMR (CD₃OD) δ ¹³ C NMR 2888, (m/z) 4.86-4.74 (m, 1H), (CD₃OD) δ 2109, [M + H]⁺ 3.95 (dd, J = 10.7, 169.74, 83.68, 1741, calcd for 7.4 Hz, 1H), 3.82 (dt, 83.52, 73.67, 1251, C₁₇H₂₈F₆NO₄, J = 9.3, 6.1 Hz, 1H), 71.42, 66.57, 1142 424.1917; 3.72 (dt, J = 9.3, 6.2 Hz, 51.36, 30.49, found, 1H), 3.64 (dt, J = 9.3, 30.29, 30.00, 424.1917 6.3 Hz, 1H), 27.01, 22.65 3.46-3.37 (m, 3H), (dd, J = 17.9, 2.34-2.15 (m, 5H), 3.2 Hz), 1.87-1.74 (m, 4H), 17.25, 16.76; 1.73-1.62 (m, 2H), ¹⁹ F NMR 1.52-1.33 (m, 2H), (CD₃OD) δ 1.42 (d, J = 6.4 Hz, 3H), −68.04 (q, J = 11.4 Hz) 0.87 (dt, J = 15.3, 4.6 Hz, 1H) F188 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³ C NMR (m/z) 8.65 (s, 3H), (CDCl₃) δ [M + H]⁺ 7.32-7.14 (m, 2H), 170.04, calcd for 7.00-6.82 (m, 3H), 157.52, C₁₈H₂₈NO₄, 4.89-4.77 (m, 1H), 129.50, 322.2013; 4.38-4.29 (m, 1H), 4.10 (t, 121.28, found, J = 8.5 Hz, 1H), 116.50, 83.15, 322.2012 3.76-3.64 (m, 1H), 82.81, 75.59, 3.56 (ddd, J = 12.4, 9.3, 73.74, 52.19, 6.8 Hz, 2H), 2.50 (t, J = 12.8 Hz, 30.81, 28.23, 1H), 23.40, 17.81, 2.26-2.03 (m, 1H), 17.77, 10.58 1.69 (tt, J = 16.1, 9.9 Hz, 3H), 1.48 (qd, J = 6.8, 2.4 Hz, 2H), 1.42 (d, J = 6.3 Hz, 3H), 0.96 (dd, J = 15.9, 6.8 Hz, 1H), 0.81 (t, J = 7.4 Hz, 3H) F189 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.63 (s, 3H), (CDCl₃) δ [M + H]⁺ 7.28-7.19 (m, 2H), 170.05, calcd for 7.03-6.77 (m, 3H), 157.51, C₂₀H₃₂NO₄, 4.83 (dd, J = 9.6, 6.3 Hz, 129.49, 350.2326; 1H), 4.34 (dt, J = 10.9, 121.26, found, 5.4 Hz, 1H), 116.46, 83.18, 350.2319 4.09 (s, 1H), 82.75, 73.99, 3.73 (dd, J = 8.9, 6.4 Hz, 73.75, 52.19, 1H), 3.64-3.44 (m, 30.81, 29.92, 2H), 2.49 (s, 1H), 28.22, 28.21, 2.31-2.02 (m, 1H), 22.42, 18.19, 1.81-1.50 (m, 3H) 17.80, 13.95. 1.43 (p, J = 7.4 Hz, 5H), 1.30-1.08 (m, 3H), 1.01-0.88 (m, 1H), 0.84 (t, J = 7.4 Hz, 1H), 0.82-0.77 (m, 2H), 0.67 (t, J = 7.4 Hz, 1H) F190 White Solid — — Ammonium Salt: — — ESIMS m/z 311.3 ([M + H]⁺) F191 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 7.32-7.23 (m, 2H), (CDCl₃) δ [M + H]⁺ 6.98 (t, J = 7.3 Hz, 169.76, calcd for 1H), 6.89 (d, J = 8.1 Hz, 156.89, C₁₉H₂₅F₃NO₄, 2H), 6.32 (dt, J = 15.8, 136.21 (q, J = 6.3 Hz), 388.1730; 2.0 Hz, 1H), 129.66, found, 5.89-5.71 (m, 1H), 122.88 (q, J = 269.0 Hz), 388.1738 4.94 (dd, J = 9.4, 6.4 Hz, 121.76, 1H), 4.42 (d, J = 15.9 Hz, 118.52 (q, J = 34.0 Hz), 2H), 116.41, 83.47, 4.34-4.20 (m, 1H), 4.01 (t, 82.35, 73.29, J = 8.7 Hz, 1H), 70.99, 51.73, 3.78-3.59 (m, 1H), 30.69, 28.06, 3.31-1.85 (m, 5H), 17.78, 17.64 1.84-1.50 (m, 3H), 1.46 (d, J = 6.3 Hz, 3H), 0.99 (dd, J = 16.4, 6.4 Hz, 1H) F192 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 7.27 (dd, J = 8.5, 7.4 Hz, (CDCl₃) δ [M + H]⁺ 2H), 6.97 (t, J = 7.4 Hz, 169.81, calcd for 1H), 157.11, C₁₉H₂₇F₃NO₄, 6.92-6.84 (m, 2H), 129.61, 390.1187; 4.88 (dt, J = 9.5, 6.3 Hz, 127.07 (q, J = 276.1 Hz), found, 1H), 4.42-4.30 (m, 121.53, 390.1889 1H), 3.99 (dd, J = 10.4, 116.17, 83.33, 7.6 Hz, 1H), 82.14, 73.59, 3.86-3.65 (m, 2H), 71.85, 51.73, 3.60 (dd, J = 9.5, 7.3 Hz, 30.73, 1H), 2.47 (dt, J = 13.6, 30.58 (q, J = 28.7 Hz), 6.8 Hz, 1H), 28.12, 2.19 (dt, J = 15.7, 7.0 Hz, 22.84 (q, J = 2.7 Hz), 1H), 2.01 (dddd, 17.72, 17.62 J = 29.9, 14.5, 7.2, 3.2 Hz, 2H), 1.80-1.60 (m, 4H), 1.56 (q, J = 11.5 Hz, 1H), 1.45 (d, J = 6.4 Hz, 3H), 0.98 (dd, J = 16.1, 7.1 Hz, 1H) F193 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.66 (s, 3H), (CDCl₃) δ [M + H]⁺ 7.28-7.16 (m, 4H), 170.06, calcd for 7.16-7.10 (m, 1H), 157.40, C₂₄H₃₂NO₄, 7.09-7.01 (m, 2H), 6.93 (t, 141.85, 398.2326; J = 7.3 Hz, 1H), 129.57, found, 6.88 (d, J = 8.0 Hz, 2H), 128.33, 398.2324 4.86 (s, 1H), 4.36 (s, 128.27, 1H), 4.10 (s, 1H), 125.73, 3.86-3.72 (m, 1H), 121.32, 3.67-3.53 (m, 2H), 116.39, 83.31, 2.54 (q, J = 13.1, 82.52, 73.72, 10.3 Hz, 3H), 2.18 (s, 73.12, 67.10, 1H), 1.77 (dq, J = 15.2, 32.30, 31.85, 8.5, 7.5 Hz, 30.84, 28.21, 5H), 1.44 (d, J = 4.9 Hz, 17.92, 17.79 3H), 0.98 (d, J = 9.1 Hz, 1H) F194 White Solid — 2923, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 1750, (m/z) 8.69 (s, 3H), (CDCl₃) δ 1507, [M + H]⁺ 7.00 (dd, J = 12.5, 8.0 Hz, 170.01, 1223 calcd for 4H), 6.92 (d, J = 8.2 Hz, 157.38, C₂₃H₃₀NO₄, 2H), 6.72 (d, J = 8.1 Hz, 155.35, 384.2169; 2H), 5.04 (br 130.96, found, s, 1H), 4.51 (t, J = 8.0 Hz, 130.94, 384.2172 1H), 4.41 (d, J = 8.4 Hz, 129.91, 1H), 129.89, 4.22-3.99 (m, 1H), 116.84, 3.82-3.74 (m, 1H), 3.70 (s, 116.38, 82.46, 3H), 2.55 (s, 1H), 82.43, 73.59, 2.24 (d, J = 8.9 Hz, 72.26, 71.12, 6H), 1.41-1.32 (m, 61.69, 59.45, 3H), 1.07 (d, J = 14.0 Hz, 52.31, 42.91, 1H) 30.95, 28.17, 20.49, 18.12, 17.87 F195 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.70 (s, 3H), (CDCl₃) δ [M + H]⁺ 7.31-7.18 (m, 2H), 7.05 (d, 170.13, calcd for J = 7.8 Hz, 2H), 159.55, C₁₈H₂₈NO₄, 6.95 (t, J = 7.3 Hz, 1H), 129.36, 322.2013; 4.97 (dt, J = 12.8, 6.4 Hz, 121.43, found, 1H), 4.36 (dd, J = 9.4, 116.41, 82.76, 322.2019 7.3 Hz, 1H), 82.67, 73.60, 4.16-4.04 (m, 1H), 71.39, 52.31, 3.60-3.48 (m, 1H), 31.03, 28.13, 3.43 (dt, J = 8.9, 6.6 Hz, 23.12, 18.01, 1H), 3.21 (dt, J = 9.0, 17.91, 10.53 6.5 Hz, 1H), 2.65-2.47 (m, 1H), 2.21 (dd, J = 15.1, 5.7 Hz, 1H), 1.77 (dd, J = 41.7, 9.2 Hz, 3H), 1.41 (h, J = 7.4 Hz, 2H), 1.34 (d, J = 6.4 Hz, 3H), 0.99 (dd, J = 15.3, 5.1 Hz, 1H), 0.75 (t, J = 7.4 Hz, 3H) F196 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 8.71 (s, 3H), 7.24 (td, (CDCl₃) δ [M + H]⁺ J = 8.9, 7.3 Hz, 4H), 170.13, calcd for 7.17-7.11 (m, 1H), 159.51, C₂₄H₃₂NO₄, 7.08-6.98 (m, 4H), 141.94, 398.2326; 6.95 (t, J = 7.3 Hz, 129.45, found, 1H), 4.98 (dq, J = 12.5, 128.39, 398.2332 6.0 Hz, 1H), 128.23, 4.46-4.33 (m, 1H), 125.67, 4.12 (s, 1H), 121.50, 3.51 (ddd, J = 12.1, 9.6, 116.28, 82.91, 5.9 Hz, 2H), 3.22 (dt, 82.28, 73.64, J = 9.1, 6.1 Hz, 1H), 68.59, 52.30, 3.03-2.52 (m, 2H), 32.14, 31.51, 2.52-2.41 (m, 2H), 31.05, 27.99, 2.33-2.11 (m, 1H), 18.01, 17.90 1.70 (dq, J = 12.8, 6.2 Hz, 4H), 1.34 (d, J = 6.3 Hz, 3H), 0.98 (d, J = 16.2 Hz, 1H) F197 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.72 (s, 3H), (CDCl₃) δ [M + H]⁺ 7.31-7.21 (m, 2H), 170.10, calcd for 6.97 (dd, J = 15.9, 7.9 Hz, 159.18, C₁₉H₂₇F₃NO₄, 3H), 5.03-4.93 (m, 129.49, 390.1187; 1H), 4.39 (t, J = 8.2 Hz, 127.14 qd, J = 276.1 Hz), found, 1H), 4.14 (s, 1H), 121.66, 390.1892 3.54 (s, 2H), 115.96, 83.18, 3.35-3.14 (m, 1H), 2.59 (s, 81.84, 73.48, 1H), 2.30-2.04 (m, 67.63, 52.32, 1H), 1.97-1.76 (m, 30.99, 3H), 1.71 (s, 2H), 30.38 (q, J = 28.9 Hz), 1.61 (p, J = 7.6, 7.0 Hz, 28.09, 2H), 1.36 (d, J = 6.0 Hz, 22.55 (q, J = 2.8 Hz), 3H), 17.94, 17.88 1.11-0.94 (m, 1H) F198 White Solid — — ESIMS — — m/z 314.3 ([M + H]⁺) F199 White Solid — — ESIMS — — m/z 382.3 ([M + H]⁺) F200 White Solid — — HRMS-ESI (m/z) ¹H NMR (CDCl₃) δ ¹³C NMR [M + H]⁺ calcd for 8.67 (s, 3H), (CDCl₃) δ C₁₈H₃₄NO₄, 4.69 (dq, J = 12.5, 6.0 Hz, 170.12, 84.08, 328.2482, 1H), 4.29 (s, 1H), 83.15, 80.97, 328.2492 4.02 (s, 1H), 75.84, 74.26, 3.41 (dd, J = 9.4, 7.0 Hz, 52.26, 32.92, 1H), 3.32-3.24 (m, 32.27, 31.05, 1H), 3.24-3.17 (m, 28.88, 27.51, 1H), 3.12 (dd, J = 8.6, 23.24, 23.16, 6.0 Hz, 1H), 19.62, 19.46, 2.51 (s, 1H), 18.05, 17.85 2.20-2.06 (m, 1H), 1.89-1.46 (m, 12H), 1.37 (d, J = 6.3 Hz, 3H), 0.90 (dd, J = 6.7, 4.2 Hz, 6H), 0.82 (d, J = 14.6 Hz, 1H) F201 White Solid — — ESIMS — — m/z 340.3 ([M + H]⁺) F202 White Solid — — ESIMS — — m/z 368.3 ([M + H]⁺) F203 White Solid — 2959, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2936, (m/z) 8.69 (br s, 3H), (CDCl₃) δ 2878, [M + H]⁺ 4.74 (t, J = 7.2 Hz, 1H), 169.99, 83.91, 1751, calcd for 4.01-3.97 (m, 1H), 83.53, 75.52, 1207 C₁₅H₃₀NO₄, 3.75 (dt, J = 8.9, 6.5 Hz, 74.21, 70.90, 288.2169; 1H), 3.51 (ddt, J = 29.8, 52.10, 31.28, found, 9.0, 6.6 Hz, 27.87, 23.49, 288.2167 2H), 3.35-3.15 (m 23.33, 17.81, 3H) 2.56-2.45 (m, 17.77, 10.76, 1H) 2.11 (s, 1H), 10.67 1.75-1.47 (m, 7H), 1.39 (d, J = 6.2 Hz, 3H), 0.92 (td, J = 7.4, 1.8 Hz, 6H), 0.86-0.71 (m, 1H) F204 White Solid — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR m/z 314 4.72 (dq, J = 9.4, 6.3 Hz, (CD₃OD) δ ([M + H]⁺) 1H), 4.32 (td, J = 4.8, 171.27, 85.26, 2.6 Hz, 1H), 84.55, 82.36, 3.94 (dd, J = 10.6, 7.0 Hz, 75.48, 71.88, 1H), 3.52 (dt, J = 8.8, 52.90, 33.91, 6.7 Hz, 1H), 3.44 (dd, 33.32, 31.94, J = 9.4, 6.9 Hz, 1H), 28.66, 24.48, 3.36-3.24 (m, 2H), 24.27, 24.25, 2.36-2.13 (m, 2H), 18.90, 18.48, 1.88-1.76 (m, 1H), 11.24 1.76-1.42 (m, 12H), 1.39 (d, J = 6.4 Hz, 3H), 0.94 (t, J = 7.4 Hz, 3H), 0.84 (dt, J = 15.9, 4.3 Hz, 1H) F205 White Solid — — ESIMS ¹H NMR (CD₃OD) δ — m/z 368 4.91-4.84 (m, 1H), ([M + H]⁺) 4.78 (ddd, J = 7.8, 6.0, 2.1 Hz, 1H), 4.21-4.11 (m, 1H), 3.97 (dd, J = 10.8, 7.1 Hz, 1H), 3.62 (dd, J = 9.4, 7.4 Hz, 1H), 2.78 (ddd, J = 15.6, 8.5, 7.2 Hz, 1H), 2.27 (dtd, J = 13.9, 7.0, 1.9 Hz, 1H), 2.17-2.04 (m, 1H), 2.00-1.90 (m, 1H), 1.90-1.79 (m, 2H), 1.79-1.45 (m, 16H), 1.44 (d, J = 6.5 Hz, 3H), 1.16-1.03 (m, 1H) F206 White Solid — 3398, ESIMS ¹H NMR (CD₃OD) δ — 2924, m/z 366 7.04-6.89 (m, 4H), 1749, ([M + H]⁺) 4.32-4.26 (m, 2H), 1503 3.99 (dd, J = 10.7, 7.2 Hz, 1H), 3.77-3.63 (m, 2H), 2.34-2.10 (m, 2H), 1.88-1.39 (m, 11H), 1.47 (d, J = 6.4 Hz, 3H), 0.98 (dd, J = 16.4, 7.6 Hz, 1H) F207 White Solid — — ESIMS — — m/z 390.4 ([M + H]⁺) F208 White Solid — — ESIMS — — m/z 342.3 ([M + H]⁺) F209 White Solid — — ESIMS — — m/z 378.3 ([M + H]⁺) F210 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR m/z 493.1 12.09 (s, 1H), (CDCl₃) δ ([M + H]⁺), 8.48 (d, J = 8.1 Hz, 1H), 172.09, m/z 515.2 7.99 (d, J = 5.2 Hz, 168.65, ([M + Na]⁺) 1H), 6.86 (d, J = 5.2 Hz, 155.34, 1H), 4.77 (dq, J = 9.7, 148.72, 6.4 Hz, 1H), 140.51, 4.58 (dt, J = 10.8, 7.7 Hz, 130.43, 1H), 3.94 (s, 3H), 109.45, 84.71, 3.69-3.58 (m, 1H), 80.34, 79.29, 3.54 (dd, J = 9.6, 7.0 Hz, 75.87, 73.45, 1H), 3.34 (t, J = 5.6 Hz, 56.07, 51.32, 1H), 3.27 (dd, 33.52, 33.35, J = 8.6, 6.7 Hz, 1H), 32.69, 28.93, 3.12 (dd, J = 8.6, 6.2 Hz, 27.45, 25.76, 1H), 2.36 (dd, J = 13.4, 24.55, 24.45, 6.5 Hz, 1H), 19.63, 19.54, 2.23-2.07 (m, 1H), 18.27, 18.25 1.98 (dd, J = 13.6, 8.8 Hz, 2H), 1.89-1.59 (m, 5H), 1.55 (d, J = 9.7 Hz, 1H), 1.45-1.31 (m, 4H), 1.31-1.10 (m, 5H), 0.92 (d, J = 6.7 Hz, 7H) F211 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR m/z 493.1 12.09 (s, 1H), (CDCl₃) δ ([M + H]⁺), 8.46 (d, J = 8.1 Hz, 1H), 172.09, m/z 515.2 7.99 (d, J = 5.2 Hz, 168.65, ([M + Na]) 1H), 6.86 (d, J = 5.2 Hz, 155.36, 1H), 4.80 (dq, J = 9.8, 148.74, 6.5 Hz, 1H), 140.50, 4.58 (dt, J = 10.8, 7.6 Hz, 130.43, 1H), 3.94 (s, 3H), 109.46, 83.81, 3.69 (dd, J = 8.5, 6.0 Hz, 80.99, 76.00, 1H), 73.61, 56.07, 3.60-3.43 (m, 1H), 3.34 (ddd, J = 8.4, 51.32, 33.78, 7.2, 3.9 Hz, 33.43, 32.32, 3H), 2.37 (dt, J = 14.0, 29.18, 29.13, 7.0 Hz, 1H), 25.78, 24.43, 2.04 (ddd, J = 21.2, 24.24, 19.63, 9.4, 5.0 Hz, 1H), 19.45, 18.50, 1.91 (t, J = 8.8 Hz, 1H), 17.93 1.83 (dt, J = 13.0, 6.6 Hz, 2H), 1.78-1.63 (m, 4H), 1.60 (s, 1H), 1.41 (d, J = 6.4 Hz, 3H), 1.38-1.12 (m, 7H), 0.91 (dd, J = 9.5, 6.7 Hz, 6H) F212 White Solid 109-111 3368, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2956, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2874, [M + Na]⁺ 8.47 (d, J = 8.1 Hz, 1H), 172.05, 1743, calcd for 7.99 (d, J = 5.2 Hz, 168.64, 1650, C₂₃H₃₆N₂NaO₇, 1H), 6.87 (d, J = 5.1 Hz, 155.34, 1528, 475.2415; 1H), 148.72, 1100 found, 4.89-4.67 (m, 1H), 4.58 (dt, J = 10.8, 140.51, 475.2419 7.6 Hz, 1H), 130.40, 3.94 (s, 3H), 109.45, 84.17, 3.83-3.69 (m, 1H), 83.73, 75.95, 3.57 (dt, J = 8.8, 6.7 Hz, 75.45, 73.30, 1H), 3.41-3.32 (m, 56.07, 51.30, 2H), 3.29 (dd, J = 8.7, 33.35, 28.87, 6.5 Hz, 1H), 27.69, 23.51, 3.13 (dd, J = 8.7, 6.3 Hz, 19.53, 19.48, 1H), 2.43-2.29 (m, 18.22, 17.91, 1H), 2.23-2.04 (m, 10.69 1H), 1.82 (hept, J = 6.6 Hz, 1H), 1.73-1.61 (m, 2H), 1.62-1.52 (m, 3H), 1.41 (d, J = 6.4 Hz, 3H), 1.40-1.31 (m, 1H), 0.97-0.84 (m, 9H) F213 White Solid 63-66 3367, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2954, (m/z) 12.06 (s, 1H), (CDCl₃) δ 2872, [M + Na]⁺ 8.44 (d, J = 8.0 Hz, 1H), 173.91, 1734, calcd for 7.99 (d, J = 5.2 Hz, 172.11, 1528, C₂₄H₃₄N₂NaO₈, 1H), 6.87 (d, J = 5.3 Hz, 168.65, 1166 501.2207; 1H), 5.16 (dd, J = 9.7, 155.37, found, 7.8 Hz, 1H), 148.76, 501.2209 4.97 (dq, J = 9.8, 6.4 Hz, 140.50, 1H), 4.62 (dt, J = 10.7, 130.36, 7.6 Hz, 1H), 109.48, 81.12, 3.94 (s, 3H), 76.34, 75.56, 3.39 (ddd, J = 7.6, 5.3, 1.9 Hz, 71.77, 56.08, 1H), 3.31 (dd, J = 8.8, 51.29, 33.33, 6.1 Hz, 1H), 28.64, 28.00, 2.99 (dd, J = 8.8, 6.8 Hz, 19.31, 19.26, 1H), 2.40 (ddd, J = 13.8, 17.98, 17.22, 7.6, 6.2 Hz, 12.87, 8.48, 1H), 2.17 (dddd, J = 15.7, 8.40 10.1, 7.9, 5.3 Hz, 1H), 1.86-1.60 (m, 4H), 1.47-1.33 (m, 1H), 1.30 (d, J = 6.4 Hz, 3H), 1.07-0.96 (m, 3H), 0.92-0.81 (m, 8H) F214 Colorless — 2949, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2871, (m/z) 8.53 (s, 1H), 8.33 (d, (CDCl₃) δ 1772, [M + Na]⁺ J = 5.5 Hz, 1H), 172.55, 1743, calcd for 7.31-7.27 (m, 2H), 162.38, 1679, C₃₁H₄₂N₂NaO₈, 7.22-7.15 (m, 3H), 159.43, 1507, 593.2833; 7.00 (d, J = 5.5Hz, 1H), 146.69, 1197 found, 4.85-4.73 (m, 1H), 142.05, 593.2832 4.59 (dt, J = 10.8, 7.7 Hz, 141.43, 1H), 3.91 (s, 3H), 137.48, 3.84 (dt, J = 9.1, 6.4 Hz, 128.35, 1H), 3.63 (dt, J = 9.1, 128.32, 6.5 Hz, 1H), 125.76, 3.41-3.31 (m, 2H), 109.77, 84.25, 3.26 (dd, J = 8.7, 6.6 Hz, 83.89, 75.83, 1H), 3.09 (dd, J = 8.8, 73.00, 72.93, 6.3 Hz, 1H), 56.28, 51.35, 2.68 (td, J = 7.6, 4.3 Hz, 33.63, 32.52, 2H), 2.40 (s, 3H), 32.01, 28.84, 2.39-2.27 (m, 1H), 27.71, 20.75, 2.19-2.04 (m, 1H), 19.54, 19.49, 1.90 (dtd, J = 8.6, 18.24, 17.98 6.7, 1.8 Hz, 2H), 1.78 (dt, J = 13.2, 6.6 Hz, 1H), 1.68-1.59 (m, 2H), 1.39 (d, J = 6.3 Hz, 3H), 1.36-1.24 (m, 2H), 0.88 (dd, J = 6.7, 2.5 Hz, 6H) F215 Colorless — 2948, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi-Solid 1769, (m/z) 8.50 (s, 1H), 8.33 (d, (CDCl₃) δ 1743, [M + H]⁺ J = 5.4 Hz, 1H), 172.55, 1679, calcd for 7.32-7.24 (m, 2H), 169.44, 1507, C₃₃H₄₇N₂O₉, 7.24-7.10 (m, 3H), 162.33, 1106 615.3276; 6.99 (d, J = 5.5 Hz, 1H), 159.44, found, 4.87-4.71 (m, 1H), 146.74, 615.3298 4.58 (dt, J = 10.8, 7.8 Hz, 142.05, 1H), 3.90 (s, 3H), 141.47, 3.87-3.74 (m, 3H), 137.33, 3.74-3.54 (m, 1H), 128.35, 3.41 (s, 3H), 128.32, 3.37-3.27 (m, 2H), 125.76, 3.27-3.20 (m, 1H), 83.90, 75.82, 109.76, 84.24, 72.99, 72.91, 3.09 (dd, J = 8.7, 6.3 Hz, 67.58, 58.80, 1H), 2.98 (t, J = 6.6 Hz, 56.31, 51.33, 2H), 2.68 (td, J = 7.8, 34.62, 33.62, 4.3 Hz, 2H), 32.52, 32.01, 2.40-2.27 (m, 1H), 29.71, 28.85, 2.18-2.04 (m, 1H), 27.70, 19.54, 1.95-1.84 (m, 2H), 19.49, 18.24, 1.78 (dt, J = 13.2, 6.6 Hz, 17.99 1H), 1.69-1.57 (m, 2H), 1.39 (d, J = 6.3 Hz, 3H), 1.36-1.18 (m, 2H), 0.88 (dd, J = 6.6, 2.6 Hz, 6H) F216 White Solid — 2954, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2874, (m/z) 8.52 (d, J = 10.1 Hz, (CDCl₃) δ 1772, [M + H]⁺ 1H), 8.33 (d, J = 5.5 Hz, 172.51, 1744, calcd for 1H), 7.00 (d, J = 5.4 Hz, 168.92, 1679, C₂₆H₃₈F₃N₂O₈, 1H), 162.40, 1508, 563.2575; 4.84-4.71 (m, 1H), 159.44, 1198 found, 4.59 (dt, J = 10.7, 7.7 Hz, 146.69, 563.2587 1H), 3.91 (s, 3H), 141.39, 3.85 (dt, J = 9.3, 6.1 Hz, 137.49, 1H), 3.67 (dt, J = 9.4, 109.79, 84.07, 6.1 Hz, 1H), 83.99, 75.64, 3.39-3.29 (m, 2H), 72.68, 71.67, 3.27 (dd, J = 8.7, 6.7 Hz, 56.29, 51.33, 1H), 3.08 (dd, J = 8.7, 33.59, 31.05, 6.2 Hz, 1H), 30.76, 28.87, 2.40 (s, 3H), 2.34 (dd, J = 13.8, 27.48, 6.7 Hz, 1H), 23.1-23.00 (m), 2.25-2.05 (m, 3H), 20.76, 19.54, 1.87-1.75 (m, 3H), 19.47, 18.18, 1.71-1.59 (m, 2H), 17.93; 1.37 (d, J = 6.4 Hz, ¹⁹F NMR 3H), 1.34-1.22 (m, (CDCl₃) δ 1H), 0.91 (dd, J = 6.7, −66.43 (t, J = 10.9 Hz) 1.3 Hz, 6H), 0.91-0.83 (m, 1H) F217 Yellow Oil — 3380, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2952, (m/z) 8.32 (d, J = 8.1 Hz, (CDCl₃) δ 1745, [M]⁺ 1H), 8.27 (d, J = 5.3 Hz, 172.74, 1677, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.23, 1504, C₂₉H₄₂N₂O₉, 1H), 5.74 (s, 162.94, 1202 562.2890; 2H), 4.73 (dq, J = 8.9, 160.25, found, 6.5 Hz, 1H), 145.71, 562.2908 4.60 (dt, J = 10.8, 7.6 Hz, 143.94, 1H), 4.33 (qd, J = 5.1, 142.41, 4.7, 3.4 Hz, 1H), 109.59, 89.52, 4.02 (qd, J = 5.4, 3.8 Hz, 83.28, 81.81, 1H), 3.91 (s, 3H), 81.07, 78.94, 3.46-3.36 (m, 2H), 73.44, 56.17, 2.37 (dtd, J = 13.5, 51.65, 33.52, 6.7, 1.6 Hz, 1H), 33.45, 32.77, 2.15-2.06 (m, 1H), 32.43, 31.73, 2.07 (s, 3H), 28.38, 23.71, 1.84-1.43 (m, 18H), 1.38 (d, J = 6.4 Hz, 23.40, 23.33, 3H), 1.32 (dt, 23.30, 20.85, J = 10.8, 2.3 Hz, 1H), 18.59, 18.08 0.90 (ddt, J = 15.8, 7.4, 1.8 Hz, 1H) F218 White Foam — 3377, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR 2955, (m/z) 8.35 (d, J = 8.0 Hz, (CDCl₃) δ 1740, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 176.29, 1679 calcd for 1H), 6.94 (d, J = 5.4 Hz, 175.57, C₃₁H₄₇N₂O₁₀, 1H), 172.73, 607.3225; 5.82-5.70 (m, 2H), 162.93, found, 5.16 (dd, J = 9.8, 7.8 Hz, 160.26, 607.3241 1H), 4.95 (dq, J = 9.8, 145.55, 6.5 Hz, 1H), 141.99, 4.63 (dt, J = 10.9, 7.6 Hz, 109.54, 89.93, 1H), 3.89 (s, 3H), 81.19, 76.12, 3.37 (ddd, J = 7.5, 75.36, 71.47, 5.3, 1.9 Hz, 1H), 56.13, 51.63, 3.27 (dd, J = 8.6, 6.3 Hz, 43.98, 33.86, 1H), 3.01-2.93 (m, 33.38, 30.13, 1H), 2.73 (p, J = 7.9 Hz, 29.76, 28.69, 1H), 2.55 (p, J = 7.0 Hz, 27.84, 25.82, 1H), 2.40 (dt, 25.72, 19.37, J = 13.7, 7.0 Hz, 1H), 19.34, 18.68, 2.22-2.10 (m, 1H), 18.04, 17.26 1.95-1.41 (m, 11H), 1.36 (q, J = 11.7 Hz, 1H), 1.26 (d, J = 7.9, 3H), 1.14 (d, J = 6.9 Hz, 6H), 1.07-0.96 (m, 1H), 0.85 (d, J = 6.7 Hz, 6H) F219 Colorless — 3367, HRMS-ESI ¹HNMR (CDCl₃) δ ¹³CNMR Oil 2949, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2870, [M + H]⁺ 8.48 (d, J = 8.2 Hz, 1H), 172.03, 1742, calcd for 7.98 (d, J = 5.1 Hz, 168.66, 1649, C₂₉H₄₁N₂O₇, 1H), 7.34-7.24 (m, 155.34, 1526, 529.2908; 2H), 7.24-7.15 (m, 148.72, 1497 found, 3H), 6.86 (d, J = 5.2 Hz, 142.00, 529.2912 1H), 4.82 (dtd, J = 12.7, 140.52, 6.3, 2.0 Hz, 130.40, 1H), 4.59 (dt, J = 10.8, 128.40, 7.6 Hz, 1H), 128.34, 3.94 (s, 3H), 125.80, 3.63 (dd, J = 8.7, 6.2 Hz, 109.47, 84.30, 1H), 3.56 (dt, J = 9.1, 83.75, 80.69, 6.4 Hz, 1H), 73.35, 68.34, 3.43-3.33 (m, 4H), 56.08, 51.31, 2.70 (dd, J = 8.8, 6.7 Hz, 49.34, 33.35, 2H), 2.37 (dtd, J = 13.7, 32.53, 31.81, 6.8, 1.6 Hz, 29.11, 27.88, 1H), 2.19-2.05 (m, 19.54, 19.49, 1H), 1.97-1.78 (m, 19.43, 18.26, 3H), 1.78-1.59 (m, 17.99 2H), 1.42 (d, J = 6.3 Hz, 3H), 1.40-1.31 (m, 1H), 0.91 (d, J = 6.6 Hz, 3H), 0.89 (d, J = 6.7 Hz, 3H), 0.90-0.87 (m, 1H) F220 White Solid 3366, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR 2954, (m/z) 12.09 (s, 1H), (CDCl₃) δ 2872, [M + H]⁺ 8.48 (d, J = 8.2 Hz, 1H), 172.03, 1742, calcd for 7.99 (d, J = 5.2 Hz, 168.65, 1649, C₂₄H₃₇N₂O₇, 1H), 6.87 (d, J = 5.2 Hz, 155.34, 1526 465.2605; 1H), 4.98 (s, 1H), 148.71, found, 4.87 (t, J = 1.8 Hz, 142.48, 465.2595 1H), 4.86-4.77 (m, 140.51, 1H), 4.59 (dt, J = 10.7, 130.38, 7.6 Hz, 1H), 112.11, 3.96 (d, J = 11.7 Hz, 109.46, 83.78, 1H), 3.94 (s, 3H), 83.60, 80.67, 3.85 (d, J = 12.0 Hz, 73.37, 73.25, 1H), 3.64 (dd, J = 8.6, 56.07, 51.31, 6.1 Hz, 1H), 33.30, 29.11, 3.48-3.33 (m, 3H), 27.97, 19.71, 2.37 (dtd, J = 13.8, 7.1, 19.53, 19.38, 6.7, 1.8 Hz, 1H), 18.28, 17.96 2.23-2.05 (m, 1H), 1.83 (dq, J = 13.8, 6.9 Hz, 1H), 1.76 (s, 3H), 1.76-1.63 (m, 2H), 1.42 (d, J = 6.4 Hz, 3H), 1.39-1.32 (m, 1H), 0.99-0.93 (m, 1H), 0.92 (d, J = 6.7 Hz, 3H), 0.90 (d, J = 6.7 Hz, 3H); F221 White Solid 129-130 3384, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³CNMR 2954, (m/z) 12.04 (s, 1H), (CDCl₃) δ 2871, [M + H]⁺ 8.49 (d, J = 8.2 Hz, 1H), 175.71, 1735, calcd for 7.99 (d, J = 5.2 Hz, 171.76, 1655, C₂₆H₃₉N₂O₈, 1H), 6.87 (d, J = 5.2 Hz, 168.68, 1526, 507.2712; 1H), 155.33, 1447 found, 4.99-4.84 (m, 2H), 148.69, 507.2701 4.61 (ddd, J = 10.8, 8.2, 140.57, 7.2 Hz, 1H), 3.94 (s, 130.32, 3H), 3.50 (dd, J = 9.5, 109.50, 82.23, 7.6 Hz, 1H), 80.27, 77.63, 3.43-3.32 (m, 2H), 73.12, 56.08, 2.80-2.66 (m, 1H), 51.21, 44.09, 2.36 (dtd, J = 13.5, 7.2, 1.4 Hz, 33.16, 30.24, 1H), 2.14 (dddd, 29.76, 29.13, J = 15.9, 10.0, 7.8, 29.01, 25.80, 5.5 Hz, 1H), 25.79, 19.36, 1.98-1.54 (m, 11H), 19.29, 18.32, 1.44 (d, J = 6.4 Hz, 3H), 17.90 1.42-1.33 (m, 1H), 1.10 (ddt, J = 16.3, 7.4, 2.2 Hz, 1H), 0.88 (d, J = 7.0 Hz, 3H), 0.86 (d, J = 6.9 Hz, 3H) F222 Colorless — 3380, HRMS-ESI ¹HNMR (CDCl₃) δ ¹³CNMR Oil 2951, (m/z) 8.32 (d, J = 8.0 Hz, (CDCl₃) δ 2871, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.63, 1748, calcd for 1H), 170.27, 1678, C₃₂H₄₅N₂O₉, 7.33-7.25 (m, 2H), 162.98, 1502 601.3127; 7.23-7.12 (m, 3H), 6.94 (d, 160.27, found, J = 5.4 Hz, 1H), 145.74, 601.3120 5.74 (s, 2H), 4.79 (ddd, J = 10.7, 143.98, 6.7, 3.7 Hz, 142.41, 1H), 4.61 (dt, J = 10.8, 142.01, 7.5 Hz, 1H), 128.40, 3.90 (s, 3H), 128.34, 3.63 (dd, J = 8.7, 6.1 Hz, 128.31, 1H), 3.56 (dt, J = 9.1, 125.77, 6.4 Hz, 1H), 109.61, 89.54, 3.43-3.30 (m, 4H), 84.37, 83.79, 2.70 (dd, J = 8.8, 6.7 Hz, 80.67, 73.07, 2H), 2.46-2.30 (m, 68.29, 56.19, 1H), 2.10 (dd, J = 5.3, 51.63, 33.42, 3.1 Hz, 1H), 32.53, 31.80, 2.07 (s, 3H), 29.10, 27.94, 1.94-1.78 (m, 4H), 20.88, 19.55, 1.78-1.57 (m, 1H), 1.40 (d, J = 6.3 Hz, 19.43, 18.32, 3H), 17.98 1.38-1.26 (m, 1H), 0.96-0.93 (m, 1H), 0.91 (d, J = 7.2 Hz, 3H), 0.89 (d, J = 6.9 Hz, 3H) F223 White Solid 35-39 3379, HRMS-ESI ¹HNMR (CDCl₃) δ ¹³CNMR 2954, (m/z) 8.34 (d, J = 8.1 Hz, (CDCl₃) δ 2872, [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 175.70, 1732, calcd for 1H), 6.96 (d, J = 5.4 Hz, 172.35, 1677, C₂₉H₄₃N₂O₁₀, 1H), 170.23, 1502 579.2910; 5.74 (s, 2H), 162.98, found, 4.97-4.84 (m, 2H), 4.63 (dt, J = 10.7, 160.23, 579.2912 7.5 Hz, 1H), 145.75, 3.91 (s, 3H), 143.90, 3.49 (dd, J = 9.6, 7.5 Hz, 142.28, 1H), 3.44-3.30 (m, 109.66, 89.44, 2H), 2.81-2.67 (m, 82.25, 80.23, 1H), 2.43-2.29 (m, 77.72, 72.81, 1H), 2.20-2.09 (m, 56.19, 51.52, 1H), 2.08 (s, 3H), 44.07, 33.19, 2.00-1.54 (m, 11H), 30.21, 29.73, 1.42 (d, J = 6.4 Hz, 29.17, 28.98, 3H), 1.40-1.29 (m, 25.77, 25.76, 1H), 1.09 (ddt, J = 16.5, 20.85, 19.34, 7.8, 2.2 Hz, 19.27, 18.36, 1H), 0.88 (d, J = 6.3 Hz, 17.87 3H), 0.86 (d, J = 6.6 Hz, 3H) F224 Colorless — 3368, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2934, (m/z) 12.09 (s, 1H), (CDCl₃) δ 1743, [M + H]⁺ 8.48 (d, J = 8.1 Hz, 1H), 172.09, 1529 calcd for 7.98 (d, J = 5.2 Hz, 168.66, C₃₀H₄₁N₂O₇, 1H), 7.33-7.23 (m, 155.33, 541.2908; 2H), 7.23-7.15 (m, 148.70, found, 3H), 6.86 (d, J = 5.2 Hz, 141.98, 541.2919 1H), 4.76 (dq, J = 9.6, 140.53, 6.4 Hz, 1H), 130.38, 4.59 (dt, J = 10.8, 7.6 Hz, 128.38, 1H), 4.37-4.26 (m, 128.34, 1H), 3.93 (s, 3H), 125.81, 3.55 (dt, J = 9.1, 6.6 Hz, 109.48, 84.32, 1H), 3.48 (dd, J = 9.6, 83.39, 81.26, 7.1 Hz, 1H), 73.54, 68.41, 3.40-3.28 (m, 2H), 56.07, 51.33, 2.80-2.61 (m, 2H), 33.31, 32.94, 2.41-2.32 (m, 1H), 32.53, 32.41, 2.16-2.05 (m, 1H), 31.77, 27.82, 1.98-1.86 (m, 2H), 23.30, 23.24, 1.86-1.46 (m, 10H), 18.29, 18.11 1.40 (d, J = 6.5 Hz, 3H), 1.38-1.29 (m, 1H), 0.96-0.86 (m, 1H) F225 Colorless — 3378, HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Oil 2939, (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ 2868, [M + H]⁺ 1H), 8.27 (d, J = 5.3 Hz, 172.69, 1748, calcd for 1H), 170.26, 1678 C₃₃H₄₅N₂O₉, 7.33-7.23 (m, 2H), 162.97, 613.3120; 7.23-7.13 (m, 3H), 6.94 (d, J = 5.4 Hz, 160.26, found, 1H), 5.74 (s, 145.73, 613.3133 2H), 4.74 (dq, J = 9.5, 143.96, 6.4 Hz, 1H), 142.41, 4.61 (dt, J = 10.7, 7.5 Hz, 142.01, 1H), 4.36-4.26 (m, 128.38, 1H), 3.90 (s, 3H), 128.32, 3.55 (dt, J = 9.0, 6.6 Hz, 125.78, 1H), 3.48 (dd, J = 9.6, 109.62, 89.52, 7.0 Hz, 1H), 84.39, 83.36, 3.41-3.27 (m, 2H), 81.32, 73.25, 2.80-2.61 (m, 2H), 68.37, 56.19, 2.45-2.31 (m, 1H), 51.66, 33.40, 2.19-2.08 (m, 1H), 32.94, 32.52, 2.07 (s, 3H), 32.40, 31.76, 1.98-1.85 (m, 2H), 27.91, 23.29, 1.85-1.45 (m, 10H), 1.39 (d, J = 6.4 Hz, 23.23, 20.88, 3H), 18.36, 18.10 1.37-1.28 (m, 1H), 0.96-0.87 (m, 1H) F226 White Solid — — ESIMS — — m/z 314.3 ([M + H]⁺) F227 Colorless — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR Oil m/z 382 4.64 (dq, J = 9.4, 6.4 Hz, (CD₃OD) δ ([M + H]⁺) 1H), 173.78, 4.23-4.18 (m, 1H), 3.85 (dd, J = 10.7, 132.81, 7.3 Hz, 1H), 130.07, 87.79, 3.59-3.50 (m, 1H), 87.15, 84.79, 3.39-3.29 (m, 2H), 78.03, 70.65, 3.27-3.22 (m, 1H), 55.37, 36.36, 2.27-2.05 (m, 4H), 35.85, 34.59, 1.77-1.67 (m, 3H), 34.42, 34.30, 1.66-1.33 (m, 10H), 34.02, 33.73, 1.31 (d, J = 6.4 Hz, 31.08, 26.75, 3H), 0.84-0.70 (m, 26.56, 26.53, 1H) 26.50, 26.47, 21.30, 20.91 F228 White Foam — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR m/z 390 7.30-7.22 (m, 2H), (CD₃OD) δ ([M + H]⁺) 7.21-7.12 (m, 3H), 171.31, 4.73 (dq, J = 9.5, 6.4 Hz, 143.33, 1H), 129.70, 4.37-4.32 (m, 1H), 3.94 (dd, J = 10.7, 129.61, 7.3 Hz, 1H), 127.05, 85.41, 3.58 (dt, J = 9.0, 6.6 Hz, 84.67, 82.45, 1H), 3.47 (dd, J = 9.5, 75.52, 69.77, 7.0 Hz, 1H), 68.43, 53.38, 3.41-3.32 (m, 2H), 34.14, 33.86, 2.79-2.61 (m, 2H), 33.60, 33.36, 2.34-2.10 (m, 2H), 32.37, 29.05, 1.97-1.76 (m, 3H), 24.51, 24.48, 1.76-1.42 (m, 10H), 19.36, 18.90 1.40 (d, J = 6.4 Hz, 3H), 0.85 (dt, J = 16.3, 4.3 Hz, 1H) F229 Colorless — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR Oil m/z 378.3 6.92-6.80 (m, 4H), (CD₃OD) δ ([M + H]⁺) 4.86-4.80 (m, 1H), 171.23, 4.31 (tt, J = 5.3, 3.5 Hz, 155.86, 1H), 4.23 (ddd, J = 7.1, 152.78, 5.3, 1.7 Hz, 118.77, 1H), 3.98 (dd, J = 10.8, 115.77, 85.04, 7.5 Hz, 1H), 84.67, 82.11, 3.74 (s, 3H), 75.39, 68.18, 3.75-3.71 (m, 1H), 56.17, 52.86, 2.26 (dt, J = 13.7, 7.1 Hz, 33.86, 33.47, 1H), 2.20-2.12 (m, 31.91, 28.98, 1H), 1.90-1.48 (m, 24.19, 24.13, 10H), 1.46 (d, J = 6.4 Hz, 18.85, 18.43 3H), 1.45-1.35 (m, 1H), 0.93 (ddt, J = 16.2, 7.7, 1.7 Hz, 1H) F230 White Foam — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR m/z 314.4 4.72 (dq, J = 9.4, 6.3 Hz, (CD₃OD) ([M + H]⁺) 1H), 4.32 (td, J = 4.8, δ 171.27, 2.6 Hz, 1H), 85.26, 84.55, 3.94 (dd, J = 10.6, 7.0 Hz, 82.36, 75.48, 1H), 3.52 (dt, J = 8.8, 71.88, 52.90, 6.7 Hz, 1H), 3.44 (dd, 33.91, 33.32, J = 9.4, 6.9 Hz, 1H), 31.94, 28.66, 3.36-3.24 (m, 2H), 24.48, 24.27, 2.36-2.13 (m, 2H), 24.25, 18.90, 1.88-1.76 (m, 1H), 18.48, 11.24 1.76-1.42 (m, 12H), 1.39 (d, J = 6.4 Hz, 3H), 0.94 (t, J = 7.4 Hz, 3H), 0.84 (dt, J = 15.9, 4.3 Hz, 1H) F231 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 7.24 (t, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 2H), 6.94 (t, J = 7.4 Hz, 175.68, calcd for 1H), 169.87, C₂₁H₃₀NO₅, 6.89-6.79 (m, 2H), 5.35 (dd, J = 9.5, 157.60, 376.2118; 8.1 Hz, 1H), 129.49, found, 5.06 (dq, J = 12.7, 6.3 Hz, 121.56, 376.2122 1H), 4.48-4.30 (m, 116.40, 79.58, 1H), 4.06 (dd, J = 10.3, 74.57, 72.42, 7.7 Hz, 1H), 51.82, 43.68, 2.56 (ddd, J = 19.5, 30.80, 29.80, 9.7, 3.9 Hz, 5H), 29.70, 28.60, 1.93-1.40 (m, 12H), 25.67, 25.58, 1.33 (d, J = 6.3 Hz, 3H), 17.51, 17.11 1.13 (dd, J = 16.0, 7.1 Hz, 1H) F232 White Tacky — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 12.03 (s, 1H), 8.45 (d, (CDCl₃) δ [M + H]⁺ J = 8.0 Hz, 1H), 175.59, calcd for 7.98 (d, J = 5.2 Hz, 1H), 172.07, C₂₈H₃₅N₂O₈, 7.27-7.22 (m, 2H), 168.71, 527.2388; 6.98-6.92 (m, 1H), 157.75, found, 6.89-6.84 (m, 3H), 155.38, 527.2400 5.40 (dd, J = 9.7, 7.9 Hz, 148.76, 1H), 5.11 (dq, J = 9.8, 140.54, 6.4 Hz, 1H), 130.29, 4.68 (dt, J = 10.7, 7.6 Hz, 129.50, 1H), 4.41 (ddd, J = 7.5, 121.51, 5.4, 1.8 Hz, 1H), 116.50, 3.94 (s, 3H), 109.53, 79.77, 2.59 (ddd, J = 15.6, 8.3, 7.1 Hz, 74.85, 71.48, 1H), 2.41 (dt, J = 13.7, 56.09, 51.27, 7.1 Hz, 1H), 43.73, 33.16, 2.32-2.18 (m, 1H), 29.84, 29.73, 2.02-1.86 (m, 1H), 28.81, 25.71, 1.80-1.37 (m, 10H), 25.62, 18.02, 1.34 (d, J = 6.4 Hz, 17.30 3H), 1.27-1.14 (m, 1H) F233 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.31 (d, J = 7.8 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 175.57, calcd for 1H), 7.25 (dd, J = 8.7, 172.67, C₃₁H₃₈N₂O₁₀, 7.4 Hz, 2H), 170.30, 599.2599; 6.97-6.91 (m, 2H), 162.99, found, 6.87 (dd, J = 8.7, 0.9 Hz, 160.30, 599.2600 2H), 5.74 (s, 2H), 157.81, 5.38 (dd, J = 9.8, 7.9 Hz, 145.70, 1H), 5.09 (dq, J = 9.8, 144.10, 6.4 Hz, 1H), 4.69 (dt, 142.24, J = 10.7, 7.5 Hz, 1H), 129.47, 4.39 (ddd, J = 7.5, 5.4, 121.44, 1.8 Hz, 1H), 3.91 (s, 116.50, 3H), 2.59 (ddd, J = 15.6, 109.66, 89.54, 8.3, 7.1 Hz, 1H), 79.80, 74.95, 2.41 (dt, J = 13.7, 7.1 Hz, 71.18, 56.20, 1H), 51.63, 43.74, 2.30-2.15 (m, 1H), 2.07 (s, 3H), 33.22, 29.84, 2.00-1.86 (m, 1H), 29.73, 28.95, 1.85-1.43 (m, 9H), 25.70, 25.61, 1.42-1.30 (m, 4H), 20.88, 18.12, 1.27-1.15 (m, 1H) 17.30 F234 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.36 (d, J = 7.9 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.27, calcd for 1H), 175.58, C₃₃H₄₃N₂O₁₀, 7.30-7.20 (m, 2H), 172.67, 627.2912; 6.99-6.91 (m, 2H), 6.87 (d, J = 7.8 Hz, 162.97, found, 2H), 5.77 (d, J = 1.2 Hz, 160.27, 627.2919 2H), 157.81, 5.39 (dd, J = 9.7, 7.9 Hz, 145.56, 1H), 5.09 (dq, J = 9.9, 144.31, 6.4 Hz, 1H), 4.68 (dt, 141.91, J = 10.7, 7.5 Hz, 1H), 129.46, 4.40 (dd, J = 6.7, 4.8 Hz, 121.43, 1H), 3.89 (s, 3H), 116.50, 2.56 (tt, J = 14.0, 7.2 Hz, 109.60, 89.89, 2H), 2.41 (dt, J = 13.8, 79.80, 74.96, 7.1 Hz, 1H), 71.16, 56.14, 2.31-2.17 (m, 1H), 51.63, 43.74, 2.01-1.85 (m, 1H), 33.85, 33.23, 1.80-1.46 (m, 9H), 29.84, 29.72, 1.43-1.28 (m, 4H), 28.94, 25.70, 1.22 (dd, J = 16.1, 7.5 Hz, 25.61, 18.68, 1H), 1.15 (d, J = 7.0 Hz, 18.12, 17.30 6H) F235 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.51 (d, J = 7.6 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 175.57, calcd for 1H), 172.56, C₃₀H₃₇N₂O₉, 7.28-7.19 (m, 2H), 7.00 (d, J = 5.5 Hz, 168.89, 569.2429; 1H), 6.94 (t, J = 7.4 Hz, 162.42, found, 1H), 159.47, 569.2427 6.89-6.82 (m, 2H), 157.81, 5.37 (dd, J = 9.8, 7.9 Hz, 146.67, 1H), 5.09 (dq, J = 9.9, 141.32, 6.4 Hz, 1H), 4.68 (dt, 137.55, J = 10.6, 7.7 Hz, 1H), 129.47, 4.39 (ddd, J = 7.5, 5.5, 121.44, 1.7 Hz, 1H), 3.90 (s, 116.50, 3H), 2.64-2.52 (m, 109.86, 79.80, 1H), 2.40 (s, 4H), 74.94, 71.21, 2.30-2.16 (m, 1H), 56.30, 51.34, 1.98-1.83 (m, 1H), 43.74, 33.48, 1.78-1.45 (m, 9H), 29.84, 29.73, 1.39-1.28 (m, 4H), 28.99, 25.70, 1.24-1.13 (m, 1H) 25.61, 20.75, 18.09, 17.28 F236 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.47 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 175.58, calcd for 1H), 172.64, C₃₂H₃₉N₂O₉, 7.26-7.20 (m, 2H), 6.99 (d, J = 5.5 Hz, 172.46, 595.2650; 1H), 6.94 (t, J = 7.3 Hz, 162.36, found, 1H), 6.86 (d, 159.52, 595.2657 J = 7.8 Hz, 2H), 157.82, 5.37 (dd, J = 9.8, 7.9 Hz, 146.58, 1H), 5.08 (dq, J = 9.8, 141.70, 6.4 Hz, 1H), 4.72 (dt, 137.51, J = 10.6, 7.7 Hz, 1H), 129.46, 4.39 (ddd, J = 7.5, 5.4, 121.43, 1.7 Hz, 1H), 3.90 (s, 116.51, 3H), 2.66-2.53 (m, 109.75, 79.82, 1H), 2.40 (dt, J = 13.9, 74.96, 71.15, 7.2 Hz, 1H), 56.32, 51.25, 2.31-2.15 (m, 1H), 43.74, 33.56, 2.02-1.84 (m, 2H), 29.84, 29.73, 1.79-1.46 (m, 9H), 29.00, 25.70, 1.32 (t, J = 6.9 Hz, 25.61, 18.10, 4H), 1.27-1.16 (m, 17.28, 13.00, 3H), 1.07 (dq, J = 7.2, 9.32 3.7 Hz, 2H) F237 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.32 (d, J = 7.9 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 175.58, calcd for 1H), 7.25 (dd, J = 8.6, 172.64, C₃₃H₄₃N₂O₁₁, 7.4 Hz, 2H), 170.09, 643.2861; 6.98-6.91 (m, 2H), 162.94, found, 6.90-6.83 (m, 2H), 5.82 (s, 160.20, 643.2874 2H), 5.39 (dd, J = 9.8, 157.80, 7.9 Hz, 1H), 5.09 (dq, 145.75, J = 9.8, 6.4 Hz, 1H), 144.05, 4.67 (dt, J = 10.7, 7.5 Hz, 142.10, 1H), 4.39 (ddd, J = 7.5, 129.47, 5.4, 1.8 Hz, 121.44, 1H), 4.10 (s, 2H), 116.50, 3.90 (s, 3H), 3.60 (q, J = 7.0 Hz, 109.76, 89.53, 2H), 79.80, 74.95, 2.59 (ddd, J = 15.6, 8.3, 7.1 Hz, 71.20, 67.79, 1H), 2.40 (dt, J = 13.8, 67.19, 56.23, 7.1 Hz, 1H), 51.62, 43.74, 2.32-2.16 (m, 1H), 33.22, 29.84, 2.01-1.85 (m, 1H), 29.73, 28.94, 1.80-1.46 (m, 9H), 25.70, 25.61, 1.43-1.30 (m, 4H), 18.11, 17.30, 1.23 (t, J = 7.0 Hz, 15.02 4H) F238 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 7.26 (t, J = 7.9 Hz, (CDCl₃) δ [M + H]⁺ 2H), 6.96 (t, J = 7.3 Hz, 174.04, calcd for 1H), 6.87 (d, J = 8.1 Hz, 169.82, C₁₉H₂₆NO₅, 2H), 5.34 (dd, 157.67, 348.1805; J = 9.4, 8.1 Hz, 1H), 129.50, found, 5.06 (dt, J = 12.7, 6.3 Hz, 121.67, 348.1807 1H), 116.61, 79.54, 4.47-4.32 (m, 1H), 4.01 (dd, J = 10.3, 74.92, 72.49, 7.6 Hz, 1H), 51.72, 30.78, 2.39 (ddt, J = 100.3, 28.74, 17.49, 15.5, 7.2 Hz, 5H), 17.05, 12.75, 1.94-1.67 (m, 2H), 8.63, 8.55 1.61 (q, J = 11.4 Hz, 1H), 1.49 (tt, J = 8.1, 4.6 Hz, 1H), 1.35 (d, J = 6.3 Hz, 3H), 1.13 (dd, J = 16.1, 6.9 Hz, 1H), 0.98-0.69 (m, 4H) F239 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR m/z 12.03 (s, 1H), 8.45 (d, (CDCl₃) δ [M + H]⁺ J = 8.0 Hz, 1H), 173.88, calcd for 7.99 (d, J = 5.2 Hz, 1H), 172.07, C₂₆H₃₁N₂O₈, 7.33-7.17 (m, 2H), 168.70, 499.2075; 7.01-6.93 (m, 1H), 157.85, found, 6.92-6.84 (m, 3H), 155.39, 499.2077 5.38 (dd, J = 9.7, 7.8 Hz, 148.77, 1H), 5.11 (dq, J = 9.8, 140.54, 6.4 Hz, 1H), 130.31, 4.67 (dt, J = 10.7, 7.6 Hz, 129.49, 1H), 4.41 (ddd, J = 7.6, 121.56, 5.5, 1.9 Hz, 1H), 116.69, 3.94 (s, 3H), 2.41 (dt, 109.53, 79.72, J = 13.7, 7.1 Hz, 1H), 75.19, 71.52, 2.33-2.19 (m, 1H), 56.09, 51.29, 2.01-1.86 (m, 1H), 33.16, 28.97, 1.75 (dt, J = 15.5, 7.7 Hz, 18.04, 17.25, 1H), 12.81, 8.58, 1.55-1.44 (m, 1H), 1.41 (d, J = 12.9 Hz, 8.50 1H), 1.35 (d, J = 6.4 Hz, 3H), 1.28-1.17 (m, 1H), 0.99-0.72 (m, 4H) F240 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR m/z 8.31 (d, J = 7.9 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.27 (d, J = 5.4 Hz, 173.86, calcd for 1H), 172.66, C₂₉H₃₅N₂O₁₀, 7.30-7.21 (m, 2H), 170.29, 571.2286; 6.99-6.92 (m, 2H), 162.99, found, 6.92-6.87 (m, 2H), 5.74 (s, 2H), 160.29, 571.2298 5.37 (dd, J = 9.7, 7.9 Hz, 157.90, 1H), 5.09 (dq, J = 9.8, 145.71, 6.4 Hz, 1H), 144.08, 4.68 (dt, J = 10.7, 7.5 Hz, 142.24, 1H), 4.40 (ddd, J = 7.6, 129.46, 5.6, 1.8 Hz, 1H), 121.50, 3.91 (s, 3H), 2.41 (dt, 116.69, J = 13.7, 7.1 Hz, 1H), 109.68, 89.52, 2.31-2.17 (m, 1H), 79.76, 75.29, 2.07 (s, 3H), 71.22, 56.20, 1.99-1.85 (m, 1H), 51.65, 33.20, 1.72 (dq, J = 15.7, 7.8 Hz, 29.11, 20.87, 1H), 1.49 (tt, J = 8.0, 18.14, 17.25, 4.6 Hz, 1H), 1.34 (d, J = 6.4 Hz, 12.81, 8.53, 4H), 8.46 1.29-1.16 (m, 1H), 0.97-0.70 (m, 4H) F241 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.36 (d, J = 7.9 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.26, calcd for 1H), 173.87, C₃₁H₃₉N₂O₁₀, 7.29-7.21 (m, 2H), 172.66, 599.2599; 6.99-6.92 (m, 2H), 6.89 (dd, J = 8.7, 162.97, found, 1.0 Hz, 2H), 160.27, 599.2596 5.77 (d, J = 1.3 Hz, 2H), 157.91, 5.37 (dd, J = 9.8, 7.8 Hz, 145.57, 1H), 5.09 (dq, J = 9.8, 144.30, 6.4 Hz, 1H), 141.91, 4.68 (dt, J = 10.7, 7.5 Hz, 129.46, 1H), 4.40 (ddd, J = 7.6, 121.49, 5.6, 1.8 Hz, 1H), 116.68, 3.89 (s, 3H), 109.61, 89.88, 2.55 (hept, J = 7.0 Hz, 1H), 79.75, 75.29, 2.41 (dt, J = 13.7, 7.1 Hz, 71.21, 56.15, 1H), 2.24 (ddt, J = 13.2, 51.65, 33.85, 9.5, 7.5 Hz, 1H), 33.21, 29.11, 2.00-1.83 (m, 1H), 18.68, 18.14, 1.72 (dq, J = 15.7, 7.9 Hz, 17.25, 12.81, 1H), 8.53, 8.46 1.55-1.45 (m, 1H), 1.34 (d, J = 6.4 Hz, 4H), 1.22 (ddd, J = 19.3, 7.3, 5.1 Hz, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.96-0.71 (m, 4H) F242 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ 13CC NMR (m/z) 8.51 (d, J = 7.6 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 173.86, calcd for 1H), 172.56, C₂₈H₃₃N₂O₉, 7.29-7.22 (m, 2H), 7.00 (d, J = 5.5 Hz, 168.89, 541.2181; 1H), 6.95 (t, J = 7.3 Hz, 162.41, found, 1H), 6.88 (d, 159.47, 541.2185 J = 8.0 Hz, 2H), 157.91, 5.35 (dd, J = 9.7, 7.8 Hz, 146.68, 1H), 5.08 (dq, J = 9.8, 141.32, 6.4 Hz, 1H), 4.67 (dt, 137.55, J = 10.5, 7.7 Hz, 1H), 129.46, 4.44-4.34 (m, 1H), 121.50, 3.90 (s, 3H), 2.40 (s, 116.68, 4H), 2.32-2.16 (m, 109.86, 79.75, 1H), 1.96-1.82 (m, 75.28, 71.25, 1H), 1.71 (dt, J = 15.5, 56.30, 51.36, 8.0 Hz, 1H), 33.46, 29.16, 1.48 (tt, J = 8.1, 4.6 Hz, 20.74, 18.11, 1H), 1.34 (t, J = 7.6 Hz, 17.23, 12.80, 4H), 8.53, 8.47 1.27-1.15 (m, 1H), 0.97-0.69 (m, 4H) F243 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.49 (d, J = 7.1 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 173.87, calcd for 1H), 172.55, C₃₀H₃₇N₂O₁₀, 7.30-7.22 (m, 2H), 6.99 (d, J = 5.5 Hz, 169.43, 585.2443; 1H), 162.36, found, 6.98-6.93 (m, 1H), 159.47, 585.2447 6.91-6.86 (m, 2H), 157.90, 5.35 (dd, J = 9.8, 7.8 Hz, 146.73, 1H), 5.08 (dq, J = 9.8, 141.34, 6.4 Hz, 1H), 4.67 (dt, 137.39, J = 10.6, 7.6 Hz, 1H), 129.46, 4.39 (ddd, J = 7.6, 5.6, 121.50, 1.8 Hz, 1H), 3.89 (s, 116.68, 3H), 3.81 (t, J = 6.6 Hz, 109.87, 79.77, 2H), 3.41 (s, 3H), 75.27, 71.22, 2.98 (t, J = 6.6 Hz, 67.57, 58.78, 2H), 2.38 (dt, J = 13.8, 56.33, 51.33, 7.1 Hz, 1H), 34.63, 33.45, 2.23 (ddt, J = 13.3, 29.12, 18.11, 9.5, 7.5 Hz, 1H), 17.22, 12.80, 1.96-1.83 (m, 1H), 8.53, 8.46 1.70 (dq, J = 15.6, 7.8 Hz, 1H), 1.48 (tt, J = 8.0, 4.6 Hz, 1H), 1.40-1.27 (m, 4H), 1.21 (ddd, J = 16.0, 6.2, 2.2 Hz, 1H), 0.96-0.70 (m, 4H) F244 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.61 (s, 3H), (CDCl₃) δ [M + H]⁺ 3.56-3.51 (m, 1H), 170.09, calcd for 2.59-2.47 (m, 1H), 142.36, C₁₄H₂₆NO₄, 2.20-1.98 (m, 1H), 1.70 (d, 112.26, 85.41, 272.1862; J = 45.2 Hz, 4H), 82.94, 73.77, found, 1.57 (d, J = 3.2 Hz, 1H), 72.99, 61.47, 272.1856 1.40 (d, J = 6.2 Hz, 52.24, 30.89, 3H), 0.96-0.78 (m, 29.38, 27.77, 1H), 4.87-4.82 (m, 19.55, 17.66 0H), 4.97 (s, 1H), 4.87 (s, 1H), 4.73 (dq, J = 12.4, 6.0 Hz, 1H), 4.11-4.01 (m, 1H), 3.95 (d, J = 12.1 Hz, 1H), 3.84 (d, J = 12.1 Hz, 1H), 3.57 (s, 3H), 3.47-3.34 (m, 1H), 3.29-3.21 (m, 1H) F245 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Foam (m/z) 12.07 (dd, J = 4.6, 0.5 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.47 (d, J = 8.1 Hz, 171.97, calcd for 1H), 7.99 (d, J = 5.2 Hz, 168.66, C₂₁H₃₀N₂NaO₇, 1H), 6.87 (d, 155.34, 445.1945; J = 5.2 Hz, 1H), 148.72, found, 4.99 (dd, J = 2.0, 0.9 Hz, 142.47, 445.1961 1H), 4.91-4.86 (m, 140.51, 1H), 4.80 (dq, J = 9.5, 130.38, 6.4 Hz, 1H), 4.59 (dt, 112.18, J = 10.8, 7.6 Hz, 1H), 109.48, 85.65, 3.98 (d, J = 12.1 Hz, 83.14, 73.10, 1H), 3.94 (s, 3H), 73.07, 61.48, 3.87 (d, J = 12.1 Hz, 1H), 56.06, 51.28, 3.59 (s, 3H), 33.33, 27.87, 3.42 (ddd, J = 7.0, 5.2, 1.7 Hz, 19.56, 18.24, 1H), 3.32 (dd, J = 9.5, 17.74 7.4 Hz, 1H), 2.38 (ddd, J = 13.9, 10.1, 4.2 Hz, 1H), 2.24-2.06 (m, 1H), 1.78 (s, 2H), 1.73-1.63 (m, 2H), 1.59 (d, J = 2.3 Hz, 1H), 1.47-1.33 (m, 4H), 1.01-0.89 (m, 1H) F246 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.67 (s, 3H), 4.73 (dq, (CDCl₃) δ [M + Na]⁺ J = 12.7, 6.2 Hz, 1H), 170.05, 85.36, calcd for 4.11-3.96 (m, 1H), 83.85, 75.84, C₁₄H₂₇NNaO₄, 3.55 (s, 3H), 73.76, 61.34, 296.1832; 3.35-3.17 (m, 3H), 52.22, 31.02 found, 3.11 (dd, J = 8.7, 6.4 Hz, 28.83, 27.72, 296.1832 1H), 2.52 (d, J = 6.8 Hz, 19.46, 19.45, 1H), 2.12 (dd, J = 15.4, 17.79, 17.71 5.7 Hz, 1H), 1.79 (ddd, J = 28.0, 13.9, 8.7 Hz, 2H), 1.61 (d, J = 7.3 Hz, 2H), 1.39 (d, J = 6.3 Hz, 3H), 0.92 (d, J = 2.7 Hz, 3H), 0.90 (d, J = 2.7 Hz, 3H), 0.87-0.76 (m, 1H) F247 Off-White — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Solid (m/z) 12.09 (s, 1H), 8.47 (d, (CDCl₃) δ [M + Na]⁺ J = 8.1 Hz, 1H), 172.00, calcd for 7.99 (d, J = 5.2 Hz, 1H), 168.65, C₂₁H₃₂N₂NaO₇, 6.87 (d, J = 5.2 Hz, 155.34, 447.2102; 1H), 4.79 (dq, J = 9.3, 148.72, found, 6.4 Hz, 1H), 4.59 (dt, 140.51, 447.2115 J = 10.8, 7.7 Hz, 1H), 130.39, 3.94 (s, 3H), 3.58 (s, 109.47, 85.55, 3H), 3.38-3.22 (m, 84.03, 75.91, 3H), 3.14 (dd, J = 8.7, 73.06, 61.37, 6.4 Hz, 1H), 2.37 (dt, 56.06, 51.29, J = 13.9, 6.3 Hz, 1H), 33.34, 28.85, 2.22-2.06 (m, 1H), 27.75, 19.48, 1.84 (dp, J = 13.2, 6.6 Hz, 19.46, 18.20, 1H), 1.69 (dd, J = 13.1, 17.79 6.0 Hz, 2H), 1.47-1.28 (m, 4H), 0.93 (d, J = 2.7 Hz, 3H), 0.92 (d, J = 2.7 Hz, 3H), 0.89 (d, J = 7.3 Hz, 1H) F248 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.66 (s, 3H), (CDCl₃) δ [M + H]⁺ 7.34-7.20 (m, 2H), 170.01, calcd for 7.02-6.84 (m, 3H), 157.46, C₁₆H₂₄NO₄, 4.83 (dd, J = 9.4, 6.3 Hz, 129.57, 294.1700; 1H), 4.38-4.25 (m, 121.36, found, 1H), 4.11 (s, 1H), 116.47, 84.83, 294.1716 3.58-3.41 (m, 4H), 82.64, 73.53, 2.50 (s, 1H), 61.41, 52.20, 2.29-2.06 (m, 1H), 1.68 (dd, J = 23.6, 30.82, 28.31, 12.8 Hz, 3H), 17.78, 17.73 1.43 (d, J = 6.2 Hz, 3H), 0.97 (dd, J = 15.6, 6.7 Hz, 1H) F249 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.06 (d, J = 0.5 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.46 (d, J = 8.1 Hz, 171.92, calcd for 1H), 7.98 (d, J = 5.2 Hz, 168.69, C₂₃H₂₈N₂NaO₇, 1H), 7.28 (dd, 157.57, 467.1789; J = 8.2, 7.3 Hz, 2H), 155.36, found, 7.01-6.90 (m, 3H), 148.74, 467.1810 6.86 (d, J = 5.2 Hz, 140.54, 1H), 4.91 (dq, J = 9.6, 130.35, 6.4 Hz, 1H), 4.64 (dt, 129.56, J = 10.7, 7.7 Hz, 1H), 121.38, 4.40-4.32 (m, 1H), 116.64, 3.94 (s, 3H), 3.56 (s, 109.50, 85.04, 4H), 2.37 (dt, J = 13.6, 82.96, 72.83, 7.1 Hz, 1H), 61.43, 56.07, 2.19 (dddd, J = 15.8, 51.23, 33.21, 10.1, 8.0, 5.4 Hz, 1H), 28.29, 18.20, 1.90-1.76 (m, 1H), 17.82 1.75-1.58 (m, 1H), 1.47 (d, J = 6.4 Hz, 3H), 1.41-1.29 (m, 1H), 1.06 (dd, J = 16.1, 7.8 Hz, 1H) F250 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.28 (d, J = 5.4 Hz, 172.58, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.25, C₂₄H₃₅N₂O₉, 1H), 5.74 (s, 162.96, 495.2337; 2H), 5.01-4.97 (m, 160.25, found, 1H), 4.91-4.86 (m, 145.73, 495.2368 1H), 4.78 (dq, J = 9.5, 143.96, 6.4 Hz, 1H), 4.61 (dt, 142.50, J = 10.8, 7.6 Hz, 1H), 142.39, 3.98 (d, J = 12.1 Hz, 112.15, 1H), 3.91 (s, 3H), 109.61, 89.51, 3.87 (d, J = 12.1 Hz, 1H), 85.69, 83.21, 3.59 (s, 3H), 3.41 (td, 73.03, 72.82, J = 6.1, 5.1, 1.7 Hz, 61.46, 56.18, 1H), 3.31 (dd, J = 9.5, 51.60, 33.40, 7.3 Hz, 1H), 29.37, 27.92, 2.45-2.32 (m, 1H), 2.07 (s, 20.86, 19.56, 4H), 1.77 (s, 2H), 18.29, 17.73 1.68 (dq, J = 15.1, 8.4 Hz, 2H), 1.59 (d, J = 2.8 Hz, 1H), 1.40 (d, J = 6.4 Hz, 4H), 0.93 (ddd, J = 14.3, 7.4, 2.3 Hz, 1H) F251 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.61, calcd for 1H), 6.95 (d, J = 5.4 Hz, 170.25, C₂₄H₃₆N₂NaO₉, 1H), 5.74 (s, 162.95, 519.2313; 2H), 4.77 (dq, J = 9.3, 160.25, found, 6.4 Hz, 1H), 4.61 (dt, 145.72, 519.2336 J = 10.8, 7.5 Hz, 1H), 143.96, 3.91 (s, 3H), 3.58 (s, 142.41, 3H), 3.30 (ddt, J = 11.6, 109.60, 89.52, 9.3, 6.4 Hz, 3H), 85.59, 84.11, 3.13 (dd, J = 8.8, 6.4 Hz, 75.88, 72.78, 1H), 2.38 (dt, J = 13.8, 61.35, 56.18, 6.7 Hz, 1H), 51.61, 33.42, 2.07 (s, 4H), 28.84, 27.81, 1.89-1.77 (m, 1H), 20.86, 19.48, 1.75-1.58 (m, 2H), 19.46, 18.26, 1.44-1.30 (m, 4H), 0.93 (d, 17.77 J = 2.9 Hz, 3H), 0.92 (d, J = 2.9 Hz, 3H), 0.88 (d, J = 7.4 Hz, 1H) F252 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.31 (d, J = 8.0 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (d, J = 5.4 Hz, 172.53, calcd for 1H), 170.27, C₂₆H₃₂N₂NaO₉, 7.31-7.24 (m, 2H), 163.00, 540.2032; 6.98-6.92 (m, 4H), 5.74 (s, 2H), 160.27, found, 4.89 (dq, J = 9.6, 6.4 Hz, 157.62, 540.2042 1H), 4.66 (dt, J = 10.7, 145.74, 7.6 Hz, 1H), 144.00, 4.40-4.32 (m, 1H), 142.34, 3.90 (s, 3H), 3.55 (s, 129.53, 4H), 2.37 (dt, J = 13.6, 121.32, 7.1 Hz, 1H), 116.65, 2.17 (ddddd, J = 15.9, 109.64, 89.51, 13.3, 10.3, 8.1, 2.7 Hz, 85.09, 83.05, 1H), 2.07 (s, 3H), 72.54, 61.42, 1.88-1.76 (m, 1H), 56.19, 51.57, 1.64 (dq, J = 15.5, 7.7 Hz, 33.28, 28.36, 1H), 1.45 (d, J = 6.4 Hz, 20.88, 18.27, 3H), 17.81 1.37-1.25 (m, 1H), 1.05 (dd, J = 16.1, 7.8 Hz, 1H) F253 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.22, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.58, C₂₆H₃₈N₂NaO₉, 1H), 162.94, 545.2470; 5.81-5.73 (m, 2H), 160.24, found, 5.01-4.96 (m, 1H), 145.59, 545.2500 4.91-4.86 (m, 1H), 144.19, 4.78 (dq, J = 9.5, 6.4 Hz, 142.50, 1H), 4.61 (dt, J = 10.7, 142.06, 7.6 Hz, 1H), 112.14, 3.98 (d, J = 12.1 Hz, 109.54, 89.88, 1H), 3.89 (s, 4H), 85.70, 83.22, 3.59 (s, 3H), 3.41 (ddd, J = 6.9, 73.03, 72.81, 5.2, 1.7 Hz, 1H), 61.46, 56.13, 3.31 (dd, J = 9.5, 7.3 Hz, 51.60, 33.84, 1H), 2.55 (hept, J = 7.0 Hz, 33.42, 29.37, 1H), 27.92, 19.57, 2.43-2.32 (m, 1H), 18.67, 18.30, 2.12 (dddd, J = 15.8, 13.7, 17.73 6.9, 4.2 Hz, 1H), 1.77 (s, 2H), 1.68 (dq, J = 15.1, 8.3 Hz, 2H), 1.59 (d, J = 2.7 Hz, 1H), 1.41 (d, J = 6.4 Hz, 3H), 1.39-1.28 (m, 1H), 1.15 (s, 3H), 1.14 (s, 3H), 1.02-0.88 (m, 1H) F254 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.37 (d, J = 8.1 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.27 (d, J = 5.4 Hz, 176.22, calcd for 1H), 6.94 (d, J = 5.4 Hz, 172.60, C₂₆H₄₀N₂NaO₉, 1H), 162.93, 547.2626; 5.81-5.73 (m, 2H), 160.24, found, 4.77 (dq, J = 9.3, 6.4 Hz, 145.59, 547.2648 1H), 4.61 (dt, J = 10.8, 144.18, 7.5 Hz, 1H), 142.08, 3.89 (s, 3H), 3.58 (s, 109.53, 89.89, 3H), 3.30 (ddt, J = 11.7, 85.60, 84.11, 9.3, 6.4 Hz, 3H), 75.88, 72.76, 3.13 (dd, J = 8.8, 6.4 Hz, 61.35, 56.12, 1H), 2.55 (hept, J = 7.0 Hz, 51.61, 33.84, 1H), 33.44, 28.84, 2.37 (dt, J = 13.8, 6.7 Hz, 27.82, 19.48, 1H), 2.12 (dddd, J = 15.7, 19.47, 18.67, 10.1, 8.3, 5.2 Hz, 18.27, 17.77 1H), 1.91-1.76 (m, 1H), 1.75-1.56 (m, 2H), 1.40 (d, J = 6.4 Hz, 3H), 1.38-1.27 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 0.93 (d, J = 3.0 Hz, 3H), 0.92 (d, J = 3.0 Hz, 3H), 0.89 (dt, J = 7.8, 1.9 Hz, 1H) F255 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.37 (d, J = 8.0 Hz, (CDCl₃) δ [M + Na]⁺ 1H), 8.26 (d, J = 5.4 Hz, 176.23, calcd for 1H), 172.53, C₂₈H₃₆N₂NaO₉, 7.33-7.23 (m, 2H), 162.97, 567.2313; 7.01-6.91 (m, 4H), 160.25, found, 5.81-5.73 (m, 2H), 4.89 (dq, J = 9.6, 157.63, 567.2346 6.4 Hz, 1H), 145.60, 4.65 (dt, J = 10.7, 7.6 Hz, 144.22, 1H), 4.39-4.32 (m, 142.01, 1H), 3.88 (s, 3H), 129.53, 3.55 (s, 4H), 2.55 (hept, J = 7.0 Hz, 121.32, 1H), 2.37 (dt, 116.65, J = 13.6, 7.0 Hz, 1H), 109.58, 89.88, 2.17 (dddd, J = 15.7, 85.09, 83.05, 10.1, 8.0, 5.4 Hz, 1H), 72.53, 61.42, 1.87-1.78 (m, 1H), 56.14, 51.57, 1.64 (dq, J = 15.5, 7.7 Hz, 33.86, 33.29, 1H), 1.45 (d, J = 6.4 Hz, 28.36, 18.68, 3H), 18.28, 17.81 1.37-1.28 (m, 1H), 1.14 (d, J = 7.0 Hz, 6H), 1.06 (dd, J = 16.1, 7.8 Hz, 1H) F256 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.52 (d, J = 6.9 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.33 (d, J = 5.4 Hz, 172.46, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.86, C₂₃H₃₃N₂O₈, 1H), 162.38, 465.2231; 5.00-4.96 (m, 1H), 159.43, found, 4.90-4.86 (m, 1H), 146.69, 465.2246 4.77 (dq, J = 9.5, 6.4 Hz, 142.49, 1H), 4.60 (dt, J = 10.7, 141.38, 7.7 Hz, 1H), 137.48, 3.98 (d, J = 12.1 Hz, 112.19, 5H), 3.58 (s, 3H), 109.81, 85.67, 3.41 (ddd, J = 7.0, 5.2, 1.7 Hz, 83.21, 73.04, 1H), 3.29 (dd, J = 9.5, 72.84, 61.46, 7.3 Hz, 1H), 56.28, 51.33, 2.40 (s, 4H), 2.11 (dddd, J = 15.7, 29.37, 27.93, 10.1, 8.5, 5.3 Hz, 20.73, 19.57, 1H), 1.77 (s, 2H), 18.26, 17.72 1.72-1.61 (m, 2H), 1.59 (d, J = 3.0 Hz, 1H), 1.39 (d, J = 6.4 Hz, 3H), 1.32 (qd, J = 10.9, 5.2 Hz, 1H), 0.97-0.87 (m, 1H) F257 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.52 (d, J = 7.2 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.48, calcd for 1H), 7.00 (d, J = 5.5 Hz, 168.85, C₂₃H₃₅N₂O₈, 1H), 4.76 (dq, 162.37, 467.2388; J = 9.4, 6.4 Hz, 1H), 159.42, found, 4.59 (dt, J = 10.7, 7.6 Hz, 146.69, 467.2414 1H), 3.90 (s, 3H), 141.39, 3.57 (s, 3H), 137.47, 3.35-3.22 (m, 3H), 109.80, 85.57, 3.13 (dd, J = 8.8, 6.4 Hz, 84.10, 75.89, 1H), 2.40 (s, 4H), 72.79, 61.33, 2.11 (tdd, J = 13.8, 6.6, 4.1 Hz, 56.27, 51.33, 1H), 1.83 (dp, J = 13.2, 33.62, 28.83, 6.6 Hz, 1H), 27.83, 20.73, 1.71-1.58 (m, 2H) 19.47, 18.22, 1.38 (d, J = 6.4 Hz, 17.75 3H), 1.36-1.24 (m, 1H), 0.93 (d, J = 3.4 Hz, 3H), 0.91 (d, J = 3.4 Hz, 3H), 0.87 (d, J = 7.4 Hz, 1H) F258 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.52 (d, J = 6.9 Hz, (CDCl₃) δ [M + H]⁺ 1H), 8.32 (d, J = 5.4 Hz, 172.41, calcd for 1H), 168.88, C₂₅H₃₁N₂O₈, 7.31-7.25 (m, 2H), 162.43, 487.2075; 7.01-6.93 (m, 4H), 4.88 (dq, J = 9.6, 159.45, found, 6.4 Hz, 1H), 157.63, 487.2095 4.64 (dt, J = 10.7, 7.6 Hz, 146.71, 1H), 4.38-4.31 (m, 141.34, 1H), 3.89 (s, 3H), 137.51, 3.55 (s, 3H), 129.54, 3.54-3.50 (m, 1H), 2.40 (s, 3H), 121.33, 2.39-2.30 (m, 1H), 116.65, 2.22-2.09 (m, 1H), 109.84, 85.07, 1.86-1.74 (m, 1H), 83.05, 72.56, 1.62 (dq, J = 15.3, 7.8 Hz, 61.42, 56.30, 1H), 1.44 (d, J = 6.4 Hz, 51.29, 33.50, 3H), 28.39, 20.75, 1.35-1.21 (m, 1H), 18.24, 17.80 1.04 (dd, J = 16.1, 7.8 Hz, 1H) F259 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.49 (s, 1H), 8.33 (d, J = 5.5 Hz, (CDCl₃) δ [M + H]⁺ 1H), 7.00 (d, 172.51, calcd for J = 5.5 Hz, 1H), 169.44, C₂₅H₃₉N₂O₉, 4.76 (dq, J = 9.4, 6.4 Hz, 162.33, 511.2681; 1H), 4.58 (dt, J = 10.7, 159.43, found, 7.8 Hz, 1H), 146.74, 511.2650 3.90 (s, 3H), 3.81 (t, J = 6.6 Hz, 141.43, 2H), 3.57 (s, 137.32, 3H), 3.41 (s, 3H), 109.77, 85.57, 3.35-3.23 (m, 3H), 84.11, 75.89, 3.13 (dd, J = 8.8, 6.4 Hz, 72.79, 67.57, 1H), 2.99 (t, J = 6.6 Hz, 61.37, 58.80, 2H), 2.34 (dt, J = 13.8, 56.32, 51.31, 6.6 Hz, 1H), 34.61, 33.63, 2.19-2.02 (m, 1H) 28.83, 27.79, 1.83 (dp, J = 13.2, 6.6 Hz, 19.48, 18.22, 1H), 17.76 1.70-1.61 (m, 2H), 1.38 (d, J = 6.4 Hz, 3H), 1.36-1.24 (m, 1H), 0.93 (d, J = 3.4 Hz, 3H), 0.91 (d, J = 3.4 Hz, 3H), 0.87 (d, J = 7.4 Hz, 1H) F260 White Foam — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.50 (s, 1H), 8.33 (d, J = 5.4 Hz, (CDCl₃) δ [M + H]⁺ 1H), 172.42, calcd for 7.30-7.26 (m, 2H), 169.44, C₂₇H₃₅N₂O₉, 7.02-6.91 (m, 4H), 162.37, 531.2350; 4.88 (dq, J = 9.7, 6.4 Hz, 159.44, found, 1H), 4.64 (dt, J = 10.6, 157.60, 531.2337 7.8 Hz, 1H), 146.75, 4.35 (t, J = 5.5 Hz, 141.36, 1H), 3.90 (s, 3H), 137.34, 3.81 (t, J = 6.6 Hz, 2H), 129.53, 3.55 (s, 4H), 3.41 (s, 121.33, 3H), 2.99 (t, J = 6.6 Hz, 116.65, 2H), 2.34 (dt, J = 13.7, 109.81, 85.04, 7.1 Hz, 1H), 83.05, 72.54, 2.23-2.09 (m, 1H), 67.57, 61.43, 1.85-1.74 (m, 1H), 58.80, 56.32, 1.60 (dd, J = 15.4, 8.5 Hz, 51.25, 34.61, 1H), 1.44 (d, J = 6.4 Hz, 33.48, 28.33, 3H), 1.28 (q, J = 11.3 Hz, 18.22, 17.78 1H), 1.04 (dd, J = 16.1, 7.8 Hz, 1H) F261 White Solid — IR HRMS-ESI — ¹⁹F NMR (Thin (m/z) (CDCl₃) δ −122.90 Film) [M]⁺ 3449, calcd for 2950, C₁₈H₂₆FNO₄, 2900, 339.1846; 1743, found, 1713, 339.1851 1504, 1203 F262 Fluffy White — — HRMS-ESI 1H NMR (CDCl₃) δ ¹⁹F NMR Solid (m/z) 12.06 (d, J = 0.6 Hz, (CDCl₃) δ −123.15 [M]⁺ 1H), 8.48 (dd, J = 8.1, calcd for 4.4 Hz, 1H), 7.98 (dd, C₂₅H₃₁FN₂O₇, J = 5.2, 4.4 Hz, 1H), 490.2115; 7.10-6.83 (m, 5H), found, 5.02 (dq, J = 9.6, 6.4 Hz, 490.2114 1H), 4.62 (ddd, J = 10.8, 8.0, 7.2 Hz, 1H), 4.35-4.22 (m, 1H), 3.93 (s, 3H), 3.55 (ddd, J = 7.3, 5.3, 1.8 Hz, 1H), 3.46 (dt, J = 9.0, 6.6 Hz, 1H), 3.23 (dt, J = 9.0, 6.5 Hz, 1H), 2.47-2.31 (m, 1H), 2.29-2.09 (m, 1H), 1.87-1.68 (m, 2H), 1.58-1.39 (m, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.04 (ddt, J = 16.1, 6.6, 2.0 Hz, 1H), 0.79 (t, J = 7.4 Hz, 3H) F263 White Solid — — ESIMS — — m/z 340 ([M + H]⁺) F264 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 12.05 (d, J = 0.6 Hz, (CDCl₃) δ [M]⁺ 1H), 8.46 (d, J = 8.2 Hz, 171.93, calcd for 1H), 7.98 (d, J = 5.2 Hz, 168.69, C₂₅H₃₁FN₂O₇, 1H), 158.77, 490.2116; 7.02-6.83 (m, 5H), 155.36, found, 4.91 (dq, J = 9.6, 6.4 Hz, 153.76 (d, J = 2.5 Hz), 490.2115 1H), 4.63 (ddd, J = 10.8, 148.73, 8.2, 7.2 Hz, 1H), 140.55, 4.26 (ddd, J = 7.1, 5.2, 130.33, 1.8 Hz, 1H), 3.94 (s, 118.01 (d, J = 7.9 Hz), 3H), 3.72 (dt, J = 9.0, 115.89 (d, J = 22.9 Hz), 6.5 Hz, 1H), 109.50, 84.31, 3.66-3.55 (m, 2H), 83.33, 75.69, 2.37 (ddd, J = 12.7, 7.6, 6.4 Hz, 73.01, 56.08, 1H), 51.21, 33.22, 2.20-2.02 (m, 1H), 28.24, 23.45, 1.89-1.75 (m, 1H), 18.19, 17.88, 1.74-1.59 (m, 1H), 10.61 1.61-1.44 (m, 5H), 1.43-1.27 (m, 1H), 1.04 (ddt, J = 16.1, 7.8, 1.8 Hz, 1H), 0.85 (t, J = 7.4 Hz, 3H) F265 Colorless — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR Semi Solid (m/z) 8.33 (d, J = 8.0 Hz, (CDCl₃) δ −123.28 [M]+calcd for 1H), 8.28 (d, J = 5.3 Hz, C₂₈H₃₅FN₂O₉, 1H), 562.2327; 7.09-6.85 (m, 5H), 5.74 (s, 2H), found, 5.00 (dq, J = 9.7, 6.4 Hz, 562.2330 1H), 4.64 (dq, J = 10.8, 7.9 Hz, 1H), 4.29 (dd, J = 9.6, 7.3 Hz, 1H), 3.91 (s, 3H), 3.54 (ddd, J = 7.2, 5.3, 1.8 Hz, 1H), 3.46 (dt, J = 9.0, 6.6 Hz, 1H), 3.22 (dt, J = 8.9, 6.4 Hz, 1H), 2.42 (dtd, J = 13.5, 6.8, 6.2, 2.0 Hz, 1H), 2.20 (dddd, J = 15.9, 10.3, 8.4, 5.4 Hz, 1H), 2.07 (s, 3H), 1.82-1.69 (m, 2H), 1.48-1.38 (m, 3H), 1.35 (d, J = 6.4 Hz, 3H), 1.09-0.97 (m, 1H), 0.78 (t, J = 7.4 Hz, 3H) F266 Colorless — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR Semi Solid (m/z) 8.53 (d, J = 8.4 Hz, (CDCl₃) δ −123.29 [M]⁺ 1H), 8.33 (dd, J = 5.5, calcd for 4.3 Hz, 1H), C₂₇H₃₃FN₂O₈, 7.09-6.84 (m, 5H), 532.2221; 4.99 (dq, J = 9.6, 6.4 Hz, found, 1H), 4.62 (ddd, J = 10.7, 532.2227 8.4, 7.2 Hz, 1H), 4.27 (dd, J = 9.6, 7.3 Hz, 1H), 3.91 (s, 3H), 3.53 (ddd, J = 7.1, 5.3, 1.8 Hz, 1H), 3.45 (dt, J = 9.0, 6.6 Hz, 1H), 3.22 (dt, J = 9.0, 6.5 Hz, 1H), 2.40 (s, 3H), 2.45-2.32 (m, 1H), 2.26-2.11 (m, 1H), 1.79-1.61 (m, 2H), 1.49-1.39 (m, 2H), 1.41-1.30 (m, 1H), 1.34 (d, J = 6.4 Hz, 3H), 1.08-0.96 (m, 1H), 0.78 (t, J = 7.4 Hz, 3H) F267 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹⁹F NMR (m/z) CDCl₃) δ 8.31 (d, J = 8.0 Hz, (CDCl₃) δ −122.93 [M]+calcd for 1H), 8.27 (d, J = 5.4 Hz, C₂₈H₃₅FN₂O₉, 1H), 562.2327; 6.99-6.92 (m, 3H), found, 6.92-6.85 (m, 2H), 5.74 (s, 562.2335 2H), 4.89 (dq, J = 9.6, 6.4 Hz, 1H), 4.65 (dt, J = 10.7, 7.6 Hz, 1H), 4.25 (ddd, J = 7.2, 5.3, 1.8 Hz, 1H), 3.91 (s, 3H), 3.72 (dt, J = 9.0, 6.5 Hz, 1H), 3.64-3.54 (m, 2H), 2.42-2.34 (m, 1H), 2.15-2.08 (m, 1H), 2.07 (s, 3H), 1.81 (dddd, J = 15.1, 11.9, 7.7, 1.6 Hz, 1H), 1.70-1.60 (m, 1H), 1.57-1.47 (m, 2H), 1.45 (d, J = 6.4 Hz, 3H), 1.31 (dddd, J = 13.4, 12.0, 10.7, 1.4 Hz, 1H), 1.04 (ddt, J = 16.4, 8.0, 1.8 Hz, 1H), 0.84 (t, J = 7.4 Hz, 3H) F268 White Solid — — ESIMS — — m/z 352 ([M + H]⁺) F269 White Solid — — ESIMS — — m/z 340 ([M + H]⁺) F270 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, (m/z) CDCl₃) δ 12.06 (d, J = 0.7 Hz, CDCl₃) [M]+calcd for 1H), 8.48 (d, J = 8.2 Hz, δ 171.99, C₂₆H₃₄N₂O₈, 1H), 7.99 (d, 168.68, 502.2315; J = 5.2 Hz, 1H), 155.37, found, 7.06-7.00 (m, 2H), 154.24, 502.2317 6.93-6.84 (m, 1H), 154.00, 6.85-6.78 (m, 2H), 148.74, 5.01 (dq, J = 9.6, 6.4 Hz, 140.54, 1H), 4.66-4.57 (m, 130.37, 1H), 4.27 (dd, J = 9.6, 117.63, 7.3 Hz, 1H), 3.94 (s, 114.44, 3H), 3.78 (s, 3H), 109.50, 84.08, 3.55 (ddd, J = 7.2, 5.2, 1.7 Hz, 83.02, 72.94, 1H), 3.46 (dt, J = 9.0, 71.36, 56.08, 6.6 Hz, 1H), 55.69, 51.30, 3.27 (dt, J = 9.0, 6.5 Hz, 33.37, 28.03, 1H), 2.45-2.35 (m, 23.20, 18.30, 1H), 2.21 (dddd, J = 15.7, 18.19, 10.60 10.1, 8.3, 5.2 Hz, 1H), 1.76 (dddd, J = 14.8, 10.4, 7.2, 4.9 Hz, 2H), 1.51-1.40 (m, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.04 (ddt, J = 16.1, 7.4, 1.9 Hz, 1H), 0.81 (t, J = 7.4 Hz, 3H) F271 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹⁹F NMR (m/z) CDCl₃) δ 12.05 (s, (CDCl₃) δ −111.78 [M]⁺ 1H), 8.47 (d, J = 8.1 Hz, calcd for 1H), 8.00 (d, J = 5.2 Hz, C₂₅H₃₁FN₂O₇, 1H), 7.21 (td, 490.2115; J = 8.4, 6.8 Hz, 1H), found, 6.89-6.82 (m, 3H), 490.2123 6.67 (tdd, J = 8.2, 2.3, 0.9 Hz, 1H), 5.03 (dq, J = 9.6, 6.4 Hz, 1H), 4.62 (dt, J = 10.8, 7.7 Hz, 1H), 4.38 (dd, J = 9.6, 7.3 Hz, 1H), 3.94 (s, 3H), 3.55 (ddd, J = 7.3, 5.2, 1.7 Hz, 1H), 3.46 (dt, J = 9.0, 6.6 Hz, 1H), 3.22 (dt, J = 9.0, 6.4 Hz, 1H), 2.46-2.37 (m, 1H), 2.21 (dddd, J = 15.8, 10.1, 8.2, 5.2 Hz, 1H), 1.76 (dddd, J = 18.3, 12.9, 7.9, 3.7 Hz, 2H), 1.49-1.40 (m, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.05 (ddt, J = 16.1, 7.4, 1.9 Hz, 1H), 0.78 (t, J = 7.4 Hz, 3H) F272 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, (m/z) CDCl₃) δ 12.05 (d, J = 0.7 Hz, CDCl₃) [M]⁺ 1H), 8.47 (d, J = 8.0 Hz, δ 171.95, calcd for 1H), 7.99 (d, 168.69, C₂₅H₃₁ClN₂O₇, J = 5.2 Hz, 1H), 160.39, 506.1820; 7.19 (t, J = 8.1 Hz, 1H), 155.38, found, 7.14 (t, J = 2.2 Hz, 148.76, 506.1825 1H), 6.99-6.91 (m, 140.55, 2H), 6.87 (d, J = 5.2 Hz, 134.69, 1H), 5.03 (dq, J = 9.6, 130.35, 6.4 Hz, 1H), 130.09, 4.62 (dt, J = 10.8, 7.6 Hz, 121.59, 1H), 4.37 (dd, J = 9.6, 117.06, 7.2 Hz, 1H), 3.94 (s, 114.74, 3H), 3.55 (ddd, J = 7.2, 109.51, 83.28, 5.2, 1.8 Hz, 1H), 82.89, 72.50, 3.46 (dt, J = 9.0, 6.6 Hz, 71.26, 56.09, 1H), 3.21 (dt, J = 9.0, 51.29, 33.32, 6.4 Hz, 1H), 27.91, 23.15, 2.46-2.36 (m, 1H), 18.29, 18.07, 2.21 (dddd, J = 15.8, 10.2, 10.56 8.3, 5.2 Hz, 1H), 1.84-1.64 (m, 2H), 1.49-1.42 (m, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.05 (ddt, J = 16.2, 7.6, 2.0 Hz, 1H), 0.79 (t, J = 7.4 Hz, 3H) F273 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, (m/z) CDCl₃) δ 12.04 (d, J = 0.7 Hz, CDCl₃) [M]⁺ 1H), 8.47 (d, J = 8.1 Hz, δ 171.94, calcd for 1H), 7.99 (d, 168.69, C₂₅H₃₁BrN₂O₇, J = 5.2 Hz, 1H), 158.88, 550.1315; 7.39-7.33 (m, 2H), 155.38, found, 7.01-6.95 (m, 2H), 6.87 (d, 148.76, 550.1320 J = 5.2 Hz, 1H), 140.55, 5.02 (dq, J = 9.5, 6.4 Hz, 132.19, 1H), 4.67-4.58 (m, 130.35, 1H), 4.34 (dd, J = 9.6, 118.27, 7.3 Hz, 1H), 3.94 (s, 113.52, 3H), 3.55 (ddd, J = 7.3, 109.52, 83.35, 5.2, 1.8 Hz, 1H), 82.88, 72.56, 3.45 (dt, J = 9.1, 6.6 Hz, 71.30, 56.09, 1H), 3.22 (dt, J = 9.0, 51.28, 33.32, 6.5 Hz, 1H), 27.95, 23.16, 2.45-2.36 (m, 1H), 18.28, 18.07, 2.21 (dddd, J = 15.8, 10.1, 10.57 8.4, 5.3 Hz, 1H), 1.75 (ttd, J = 15.3, 7.2, 5.3 Hz, 2H), 1.51-1.38 (m, 3H), 1.34 (d, J = 6.4 Hz, 3H), 1.04 (ddt, J = 16.2, 7.2, 2.0 Hz, 1H), 0.78 (t, J = 7.4 Hz, 3H) F274 Colorless — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, Semi Solid (m/z) CDCl₃) δ 8.53 (s, 1H), CDCl₃) [M]⁺ 8.33 (d, J = 5.4 Hz, δ 172.49, calcd for 1H), 7.06-7.01 (m, 168.90, C₂₈H₃₆N₂O₉, 2H), 7.00 (d, J = 5.5 Hz, 162.41, 544.2421; 1H), 159.45, found, 6.85-6.78 (m, 2H), 4.98 (dq, J = 9.5, 154.21, 544.2427 6.4 Hz, 1H), 154.04, 4.67-4.58 (m, 1H), 146.70, 4.25 (dd, J = 9.6, 7.3 Hz, 141.40, 1H), 3.90 (s, 3H), 137.51, 3.77 (s, 3H), 3.54 (ddd, J = 7.2, 117.64, 5.3, 1.8 Hz, 1H), 114.43, 3.45 (dt, J = 9.1, 6.7 Hz, 109.82, 84.14, 1H), 3.26 (dt, J = 9.1, 83.10, 72.68, 6.5 Hz, 1H), 71.34, 56.29, 2.39 (s, 3H), 55.69, 51.36, 2.39-2.34 (m, 1H), 33.67, 28.12, 2.23-2.13 (m, 1H), 23.19, 20.75, 1.78-1.66 (m, 2H), 18.34, 18.17, 1.51-1.40 (m, 2H), 1.35 (d, J = 6.4 Hz, 10.59 3H), 1.38-1.31 (m, 1H), 1.02 (ddt, J = 16.3, 7.7, 2.0 Hz, 1H), 0.80 (t, J = 7.4 Hz, 3H) 7.4 Hz, 3H) F275 Light — — HRMS-ESI ¹H NMR (600 MHz, ¹⁹F NMR Yellow Semi (m/z) CDCl₃) δ 8.53 (s, 1H), (CDCl₃) δ −111.83 Solid [M]⁺ 8.34 (d, J = 5.4 Hz, calcd for 1H), 7.24-7.16 (m, C₂₇H₃₃FN₂O₈, 1H), 7.01 (d, J = 5.5 Hz, 532.2221; 1H), found, 6.88-6.80 (m, 2H), 6.66 (tdd, J = 8.3, 532.2231 2.4, 0.9 Hz, 1H), 5.00 (dq, J = 9.5, 6.4 Hz, 1H), 4.63 (ddd, J = 10.7, 8.4, 7.3 Hz, 1H), 4.38-4.31 (m, 1H), 3.91 (s, 3H), 3.53 (ddd, J = 7.2, 5.3, 1.9 Hz, 1H), 3.45 (dt, J = 9.0, 6.5 Hz, 1H), 3.21 (dt, J = 9.0, 6.5 Hz, 1H), 2.44-2.40 (m, 1H), 2.40 (s, 3H), 2.24-2.12 (m, 1H), 1.79-1.67 (m, 2H), 1.49-1.28 (m, 3H), 1.33 (dd, J = 6.5, 4.6 Hz, 3H), 1.03 (ddt, J = 16.2, 7.7, 2.0 Hz, 1H), 0.77 (t, J = 7.4 Hz, 3H) F276 White Solid — — ESIMS — — m/z 356 ([M + H]⁺) F277 White Solid — — ESIMS — — m/z 400 ([M + H]⁺) F278 White Solid — — ESIMS — — m/z 340 ([M + H]⁺) F279 White Solid — — ESIMS — — m/z 350 ([M + H]⁺) F280 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹⁹F NMR (m/z) CDCl₃) δ 12.05 (d, J = 0.7 Hz, (CDCl₃) δ −111.63 [M]⁺ 1H), 8.47 (d, J = 8.2 Hz, calcd for 1H), 7.99 (d, C₂₅H₃₁FN₂O₇, J = 5.2 Hz, 1H), 490.2115; 7.25-7.17 (m, 1H), found, 6.89-6.83 (m, 1H), 490.2124 6.75-6.62 (m, 3H), 4.92 (dq, J = 9.6, 6.3 Hz, 1H), 4.68-4.60 (m, 1H), 4.35 (ddd, J = 7.2, 5.3, 1.8 Hz, 1H), 3.94 (s, 3H), 3.73-3.53 (m, 3H), 2.42-2.33 (m, 1H), 2.18 (dddd, J = 15.8, 10.1, 7.9, 5.3 Hz, 1H), 1.87-1.74 (m, 1H), 1.71-1.61 (m, 1H), 1.56-1.47 (m, 2H), 1.47 (d, J = 6.4 Hz, 3H), 1.43-1.31 (m, 1H), 1.09 (ddt, J = 16.3, 8.0, 1.8 Hz, 1H), 0.82 (t, J = 7.4 Hz, 3H) F281 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, (m/z) CDCl₃) δ 12.07 (d, J = 0.7 Hz, CDCl₃) [M]⁺ 1H), 8.46 (d, J = 8.2 Hz, δ 171.96, calcd for 1H), 7.98 (d, 168.69, C₂₇H₃₆N₂O₇, J = 5.2 Hz, 1H), 157.61, 500.2523; 6.86 (d, J = 5.2 Hz, 1H), 155.36, found, 6.63-6.55 (m, 3H), 148.74, 500.2533 4.91 (dq, J = 9.6, 6.4 Hz, 140.53, 1H), 4.63 (dt, J = 10.7, 139.22, 7.7 Hz, 1H), 130.38, 4.35 (ddd, J = 7.1, 5.2, 123.15, 1.7 Hz, 1H), 3.94 (s, 114.49, 3H), 3.74 (dt, J = 9.0, 109.49, 83.32, 6.5 Hz, 1H), 83.10, 75.57, 3.66-3.55 (m, 2H), 73.09, 56.08, 2.40-2.32 (m, 1H), 2.27 (s, 51.24, 33.26, 6H), 2.23-2.13 (m, 28.13, 23.46, 1H), 1.86-1.77 (m, 21.42, 18.18, 1H), 1.71-1.60 (m, 17.94, 10.63 1H), 1.59-1.47 (m, 2H), 1.47 (d, J = 6.4 Hz, 3H), 1.39-1.29 (m, 1H), 1.01 (ddt, J = 16.4, 8.2, 1.7 Hz, 1H), 0.85 (t, J = 7.4 Hz, 3H) F282 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, (m/z) CDCl₃) δ CDCl₃) [M]⁺ 8.53-8.50 (m, 1H), 8.32 (d, J = 5.4 Hz, δ 172.45, calcd for 1H), 6.99 (d, J = 5.5 Hz, 168.89, C₂₉H₃₈N₂O₈, 1H), 162.42, 542.2628; 6.62-6.55 (m, 3H), 159.45, found, 4.88 (dq, J = 9.5, 6.4 Hz, 157.66, 542.2632 1H), 4.64 (ddd, J = 10.7, 146.70, 8.5, 7.4 Hz, 1H), 141.38, 4.33 (ddd, J = 7.2, 5.3, 139.19, 1.8 Hz, 1H), 3.89 (s, 137.51, 3H), 3.74 (dt, J = 9.0, 123.10, 6.5 Hz, 1H), 114.51, 3.64-3.54 (m, 2H), 2.40 (s, 109.82, 83.36, 3H), 2.34 (dt, J = 13.8, 83.22, 75.55, 7.1 Hz, 1H), 72.82, 56.29, 2.27 (s, 6H), 51.29, 33.56, 2.22-2.10 (m, 1H), 28.22, 23.47, 1.82-1.73 (m, 1H), 21.41, 20.75, 1.67-1.57 (m, 1H), 18.22, 17.92, 1.58-1.45 (m, 2H), 1.44 (d, 10.62 J = 6.4 Hz, 3H), 1.32-1.22 (m, 1H), 1.00 (ddt, J = 16.3, 8.1, 1.7 Hz, 1H), 0.85 (t, J = 7.4 Hz, 3H) F283 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, (m/z) CDCl₃) δ 12.06 (d, J = 0.6 Hz, CDCl₃) [M]⁺ 1H), 8.49 (d, J = 8.1 Hz, δ 172.00, calcd for 1H), 168.69, C₃₁H₃₆N₂O₇, 8.03-7.97 (m, 1H), 159.28, 548.2523; 7.59-7.54 (m, 2H), 155.38, found, 7.54-7.48 (m, 2H), 148.76, 548.2520 7.45-7.38 (m, 2H), 140.78, 7.34-7.28 (m, 1H), 140.54, 7.18-7.11 (m, 2H), 134.42, 6.89-6.84 (m, 1H), 130.38, 5.06 (dq, J = 9.6, 6.4 Hz, 128.70, 1H), 4.64 (dt, J = 10.8, 128.05, 7.7 Hz, 1H), 126.76, 4.48-4.39 (m, 1H), 126.70, 3.94 (s, 3H), 116.74, 3.63-3.54 (m, 1H), 3.47 (dt, 109.50, 83.09, J = 9.0, 6.6 Hz, 1H), 82.99, 72.83, 3.27 (dt, J = 9.0, 6.5 Hz, 71.44, 56.09, 1H), 51.32, 33.39, 2.47-2.35 (m, 1H), 2.23 (dddd, J = 15.8, 28.13, 23.19, 10.4, 8.2, 5.3 Hz, 18.34, 18.15, 1H), 10.58 1.81-1.71 (m, 2H), 1.52-1.42 (m, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.08 (ddt, J = 16.2, 7.9, 2.0 Hz, 1H), 0.79 (t, J = 7.4 Hz, 3H) F284 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR (m/z) 8.53 (d, J = 8.3 Hz, (CDCl₃) δ −111.69 [M]⁺ 1H), 8.33 (d, J = 5.4 Hz, calcd for 1H), C₂₇H₃₃FN₂O₈, 7.26-7.14 (m, 1H), 7.00 (d, J = 5.5 Hz, 532.2221; 1H), found, 6.75-6.60 (m, 3H), 532.2230 4.90 (dq, J = 9.6, 6.4 Hz, 1H), 4.64 (ddd, J = 10.7, 8.4, 7.3 Hz, 1H), 4.34 (ddd, J = 7.2, 5.3, 1.8 Hz, 1H), 3.90 (s, 3H), 3.73-3.50 (m, 3H), 2.40 (s, 3H), 2.39-2.30 (m, 1H), 2.20-2.08 (m, 1H), 1.85-1.71 (m, 1H), 1.69-1.56 (m, 1H), 1.54-1.45 (m, 2H), 1.44 (d, J = 6.4 Hz, 3H), 1.37-1.22 (m, 1H), 1.07 (ddt, J = 16.3, 7.9, 2.0 Hz, 1H), 0.82 (t, J = 7.4 Hz, 3H) F285 White Solid — — HRMS-ESI ¹H NMR (600 MHz, ¹³C NMR (151 MHz, (m/z) CDCl₃) δ 8.53 (s, 1H), CDCl₃) [M]⁺ 8.33 (d, J = 5.5 Hz, δ 172.43, calcd for 1H), 7.39-7.31 (m, 168.89, C₂₇H₃₃BrN₂O₈, 2H), 7.00 (d, J = 5.4 Hz, 162.41, 592.1427; 1H), 159.46, found, 6.99-6.96 (m, 2H), 4.99 (dq, J = 9.5, 158.91, 592.1420 6.4 Hz, 1H), 146.69, 4.62 (ddd, J = 10.7, 8.3, 7.3 Hz, 141.35, 1H), 137.53, 4.35-4.27 (m, 1H), 3.90 (s, 3H), 132.16, 3.53 (ddd, J = 7.3, 5.3, 118.29, 1.8 Hz, 1H), 3.44 (dt, 113.46, J = 9.0, 6.6 Hz, 1H), 109.85, 83.40, 3.20 (dt, J = 9.1, 6.5 Hz, 82.94, 72.29, 1H), 2.39 (s, 3H), 71.27, 56.30, 2.43-2.31 (m, 1H), 51.33, 33.60, 2.23-2.09 (m, 1H), 28.04, 23.14, 1.71 (qdt, J = 12.6, 20.75, 18.31, 5.6, 3.2 Hz, 2H), 18.04, 10.56 1.48-1.33 (m, 3H), 1.32 (d, J = 6.3 Hz, 3H), 1.03 (ddt, J = 16.2, 7.4, 2.0 Hz, 1H), 0.77 (t, J = 7.4 Hz, 3H) F286 White Solid — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (m/z) 8.53 (d, J = 8.5 Hz, (CDCl₃) δ [M]⁺ 1H), 8.38-8.30 (m, 172.45, calcd for 1H), 7.18 (t, J = 8.1 Hz, 168.90, C₂₇H₃₃ClN₂O₈, 1H), 7.13 (t, J = 2.2 Hz, 162.41, 548.1925; 1H), 7.01 (d, J = 5.5 Hz, 160.42, found, 1H), 159.46, 548.1924 6.95 (dddd, J = 9.8, 7.9, 146.70, 2.2, 0.9 Hz, 2H), 141.37, 5.00 (dq, J = 9.7, 6.4 Hz, 137.53, 1H), 4.70-4.57 (m, 134.66, 1H), 4.35 (dd, J = 9.7, 130.07, 7.2 Hz, 1H), 3.91 (s, 121.53, 3H), 3.59-3.50 (m, 117.09, 1H), 3.50-3.40 (m, 114.72, 1H), 3.20 (dt, J = 8.9, 109.83, 83.34, 6.5 Hz, 1H), 82.97, 72.23, 2.45-2.30 (m, 1H), 2.40 (s, 71.24, 56.30, 3H), 2.26-2.11 (m 51.34, 33.61, 1H), 1.81-1.65 (m, 28.01, 23.14, 2H), 1.53-1.36 (m, 20.75, 18.32, 3H), 1.35-1.28 (m, 18.05, 10.55 3H), 1.09-0.96 (m, 1H), 0.78 (t, J = 7.4 Hz, 3H) F287 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR m/z 590 8.58-8.45 (m, 1H), (CDCl₃) δ ([M − H]⁻) 8.34 (dd, J = 5.5, 1.4 Hz, 172.51, 1H), 168.91, 7.60-7.48 (m, 4H), 7.41 (td, J = 8.6, 162.42, 8.0, 2.0 Hz, 2H), 159.46, 7.30 (tt, J = 6.8, 1.4 Hz, 159.32, 1H), 146.71, 7.19-7.11 (m, 2H), 141.40, 7.04-6.96 (m, 1H), 5.03 (dq, J = 10.1, 140.80, 6.4 Hz, 1H), 137.53, 4.64 (dt, J = 11.1, 7.8 Hz, 134.37, 1H), 4.43 (dd, J = 9.7, 128.70, 7.1 Hz, 1H), 128.03, 3.90 (d, J = 1.4 Hz, 3H), 126.76, 3.64-3.51 (m, 1H), 126.68, 3.46 (dt, J = 9.5, 6.6 Hz, 116.76, 1H), 3.26 (dt, J = 9.4, 109.83, 83.16, 6.6 Hz, 1H), 83.07, 72.56, 2.40 (s, 3H), 71.41, 56.30, 2.43-2.31 (m, 1H), 51.38, 33.67, 2.25-2.13 (m, 2H), 28.21, 23.18, 1.84-1.67 (m, 2H), 20.76, 18.38, 1.48-1.40 (m, 2H), 1.37 (d, J = 6.0 Hz, 18.13, 10.57 3H), 1.12-1.00 (m, 1H), 0.78 (t, J = 7.3 Hz, 3H) F288 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR m/z 513.5 12.06 (d, J = 0.7 Hz, (CDCl₃) δ ([M + H]⁺) 1H), 8.48 (d, J = 8.1 Hz, 171.99, 1H), 8.00 (d, J = 5.2 Hz, 168.68, 1H), 159.21, 7.44-7.31 (m, 2H), 155.38, 7.07-7.00 (m, 2H), 148.75, 6.93-6.83 (m, 1H), 142.53, 5.30 (dd, J = 1.6, 0.8 Hz, 140.54, 1H), 5.09-4.97 (m, 134.37, 2H), 4.62 (dt, J = 10.8, 130.37, 7.6 Hz, 1H), 126.49, 4.48-4.34 (m, 1H), 116.08, 3.94 (s, 3H), 110.81, 3.57 (ddd, J = 7.1, 5.3, 1.8 Hz, 109.50, 83.03, 1H), 3.45 (dt, J = 9.1, 82.91, 72.83, 6.6 Hz, 1H), 71.43, 56.09, 3.26 (dt, J = 9.1, 6.5 Hz, 51.31, 33.38, 1H), 2.42 (ddd, J = 14.8, 28.12, 23.18, 7.2, 5.3 Hz, 1H), 21.90, 18.32, 2.29-2.15 (m, 1H) 18.11, 10.57 2.15-2.11 (m, 3H), 1.87-1.71 (m, 2H), 1.52-1.41 (m, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.11-1.00 (m, 1H), 0.78 (t, J = 7.4 Hz, 3H) F289 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (151 MHz, m/z 555.6 8.54 (d, J = 7.9 Hz, CDCl₃) ([M + H]⁺) 1H), 8.34 (d, J = 5.4 Hz, δ 172.49, 1H), 168.90, 7.53-7.31 (m, 2H), 162.41, 7.13-6.93 (m, 3H) 5.30 (dd, J = 1.6, 159.46, 0.9 Hz, 1H), 159.25, 5.19-4.94 (m, 2H), 146.70, 4.78-4.57 (m, 1H), 142.55, 4.48-4.19 (m, 1H), 3.90 (s, 141.39, 3H), 3.65-3.37 (m, 134.32, 2H), 3.30-3.17 (m, 129.33, 1H), 2.40 (s, 3H), 126.48, 2.45-2.31 (m, 1H), 116.49, 2.23-2.14 (m, 1H), 116.09, 2.14-2.05 (m, 3H), 110.77, 1.71 (ddd, J = 17.7, 9.4, 4.1 Hz, 109.83, 83.09, 2H), 82.98, 72.57, 1.53-1.30 (m, 3H), 1.34 (d, J = 6.4 Hz, 71.41, 56.29, 3H), 51.37, 33.66, 1.04 (ddd, J = 16.3, 5.9, 3.8 Hz, 28.21, 23.17, 1H), 20.75, 18.36, 0.88-0.64 (m, 3H) 18.08, 10.56 F290 White Solid — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR m/z 545.5 12.02 (d, J = 0.6 Hz, (CDCl₃) δ ([M + H]⁺) 1H), 8.50 (d, J = 8.1 Hz, 171.75, 1H), 7.99 (d, J = 5.2 Hz, 168.73, 1H), 6.87 (dd, 159.07, J = 5.3, 0.6 Hz, 1H), 155.37, 6.65-6.60 (m, 3H), 154.41, 5.12 (dq, J = 9.5, 6.4 Hz, 148.74, 1H), 5.00 (ddd, J = 7.7, 140.59, 5.5, 2.1 Hz, 139.27, 1H), 4.66 (ddd, J = 10.8, 130.29, 8.2, 7.2 Hz, 1H), 123.68, 4.50 (dd, J = 9.5, 7.7 Hz, 114.01, 1H), 109.54, 80.79, 4.01-3.92 (m, 2H), 3.94 (s, 3H), 80.60, 72.57, 2.43 (dtd, J = 13.7, 69.61, 56.09, 7.1, 6.7, 2.0 Hz, 1H), 51.22, 33.18, 2.28 (s, 6H), 29.42, 21.89, 2.26-2.18 (m, 1H), 21.40, 18.37, 1.93-1.75 (m, 2H), 18.04, 10.03 1.63-1.43 (m, 3H), 1.41 (d, J = 6.4 Hz, 3H), 1.30 (td, J = 6.8, 6.3, 3.4 Hz, 1H), 0.84 (t, J = 7.4 Hz, 3H) F291 Colorless — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR Semi Solid (m/z) 8.56 (d, J = 8.4 Hz, (CDCl₃) δ [M]⁺ 1H), 8.34 (d, J = 5.4 Hz, 172.23, calcd for 1H), 7.01 (d, J = 5.5 Hz, 168.89, C₃₀H₃₈N₂O₁₀, 1H), 162.45, 586.2532; 6.65-6.59 (m, 3H), 159.45, found, 5.16-5.06 (m, 1H), 159.09, 586.2526 5.06-4.94 (m, 1H), 154.42, 4.66 (ddd, J = 10.7, 8.3, 7.1 Hz, 146.72, 1H), 141.28, 4.53-4.43 (m, 1H), 3.95 (tdt, J = 4.9, 139.25, 2.5, 1.0 Hz, 3H), 137.52, 3.91 (s, 3H), 123.64, 2.47-2.34 (m, 1H), 2.40 (s, 114.03, 3H), 2.28 (d, J = 0.8 Hz, 109.86, 80.86, 6H), 80.70, 72.31, 2.24-2.15 (m, 1H), 69.59, 56.30, 1.83-1.75 (m, 1H), 51.28, 33.46, 1.59-1.50 (m, 2H), 1.39 (d, J = 6.4 Hz, 29.51, 21.88, 3H), 21.40, 20.75, 1.31-1.21 (m, 2H), 0.83 (t, 18.41, 18.02, J = 7.4 Hz, 3H) 10.03 F292 White Solid — — ESIMS — — m/z 398 ([M + H]⁺) F293 White Solid — — ESIMS — — m/z 394 ([M + H]⁺) F294 White Solid — — ESIMS — — m/z 362 ([M + H]⁺) *Cmpd. No.—Compound Number *Phys. App.—Physical Appearance *MP—Melting Point; ° C. *IR—Infrared Spectroscopy; Thin Film; cm⁻¹ *¹H NMR were run at 400 MHz unless specified otherwise. *¹³C NMR were run at 101 MHz unless specified otherwise. *¹⁹F NMR were run at 376 MHz unless specified otherwise.

TABLE 3 Rating Scale for Results of Biological Evaluation Biology Rating Table (% Control) Rating 80-100 A More than 0-Less than 80 B Not Tested C ≦0 D

TABLE 4 Biological Activity - Disease Control in High Volume Applications (100 ppm) Compound PUCCRT SEPTTR Number 1DP 3DC 1DP 3DC F1 C C C C F2 C C C C F3 C C C C F4 C C C C F5 C C C C F6 C C C C F7 C C C C F8 C C C C F9 C C C C F10 C C C C F11 C C C C F12 C C C C F13 C C C C F14 A A D A F15 A A A A F16 A A A A F17 A A A A F18 A A A A F19 A A A A F20 A A A A F21 A A B B F22 A A A A F23 A A A A F24 A A A A F25 A A A A F26 A A A A F27 A A A A F28 A A A A F29 A A A A F30 A A A B F31 A A A A F32 A A A A F33 A A B A F34 A A A A F35 A A A A F36 A A A A F37 A A A A F38 A A A A F39 A A A A F40 A A B B F41 A A B A F42 A A A A F43 A A A A F44 A A A A F45 A A A A F46 A A A A F47 A A A A F48 A A A A F49 A A A A F50 A A A B F51 A A A A F52 A A A A F53 A A A B F54 A A A B F55 A A A A F56 A A A A F57 A A A A F58 A A A A F59 A A A A F60 A A A A F61 A A A A F62 A A A A F63 A A A A F64 B D B B F65 A A A B F66 A A A B F67 A A A B F68 A A A A F69 A A A A F70 B B B B F71 B A B B F72 A A A A F73 A A B A F74 A A A A F75 A A A A F76 A A A A F77 A A A A F78 A A A A F79 A A A A F80 A A A A F81 A A A A F82 B B D B F83 A A A A F84 B B B B F85 D B D B F86 A A A A F87 A A A A F88 A A A A F89 A A A A F90 A A A A F91 A A A A F92 A A A A F93 A A A A F94 B D B B F95 A A A A F96 A A A A F97 A A A A F98 A A A A F99 A A A A F100 A A A A F101 A A A A F102 A A A A F103 A A A A F104 A D A D F105 A D A B F106 A A A A F107 A A A A F108 A A A A F109 A A A A F110 A A A A F111 A D B B F112 A A A A F113 B B D B F114 A A A A F115 A B A B F116 A A A A F117 A A D A F118 A A A B F119 A A A A F120 A A A A F121 A A A A F122 A A A A F123 A A A A F124 A A A A F125 A A A A F126 A A A A F127 A A A A F128 A B A D F129 A A A D F130 A A A A F131 A A A A F132 A A A A F133 A A A A F134 A A A A F135 A A A A F136 A A A A F137 A A A A F138 A A A A F139 A A A A F140 A A A A F141 A A A A F142 A A B A F143 A A A B F144 A A A A F145 A A A A F146 A A A A F147 A A A A F148 A A A A F149 A A A B F150 A A A A F151 A A A A F152 A A A A F153 A A A A F154 A A A A F155 A A A A F156 A A A A F157 A A A A F158 A A A A F159 A A A A F160 A A A A F161 A A A A F162 A B A A F163 A A A B F164 A A A A F165 A A A A F166 A A A A F167 A A A A F168 A A A A F169 A A A A F170 A A A A F171 A A A A F172 A A A A F173 A A A A F174 C C C C F175 C C C C F176 C C C C F177 C C C C F178 C C C C F179 C C C C F180 C C C C F181 C C C C F182 C C C C F183 C C C C F184 C C C C F185 C C C C F186 C C C C F187 C C C C F188 C C C C F189 C C C C F190 C C C C F191 C C C C F192 C C C C F193 C C C C F194 C C C C F195 C C C C F196 C C C C F197 C C C C F198 C C C C F199 C C C C F200 C C C C F201 C C C C F202 C C C C F203 C C C C F204 C C C C F205 C C C C F206 C C C C F207 C C C C F208 C C C C F209 C C C C F210 A A A A F211 A A A A F212 A A B B F213 A A B B F214 A A A A F215 A A A A F216 A A A A F217 A A A A F218 A A A B F219 A A A B F220 A A A A F221 A B A B F222 A A A A F223 A A A A F224 A B B B F225 A A A A F226 C C C C F227 C C C C F228 C C C C F229 C C C C F230 C C C C PUCCRT - Wheat brown rust (Puccinia triticina) SEPTTR - Wheat leaf blotch (Septoria tritici) 1DP—1 Day Protectant 3DC—3 Day Curative

TABLE 5 Biological Activity-Disease Control in High Volume (100 ppm) and Low Volume Applications (121.5 g/H) PUCCRT* SEPTTR* 1DP* 3DC* 1DP* 3DC* Rate Rate Compound 121.5 g/ 100 121.5 g/ 100 121.5 g/ 100 121.5 g/ 100 Number H* ppm* H* ppm* H* ppm* H* ppm* F231 C C C C C C C C F232 C A C A C A C B F233 A A B A A A A A F234 A A D A A A D A F235 A A B A A A B A F236 B A D B A B B B F237 A A B A D B B B F238 C C C C C C C C F239 C B C D C D C B F240 A A A A A A A A F241 A A A A D A D A F242 A A B A B A B A F243 A A A A B A A A F244 C C C C C C C C F245 C A C B C B C A F246 C C C C C C C C F247 C A C A C A C B F248 C C C C C C C C F249 C A C A C B C B F250 B C A C D C B C F251 A C A C D C D C F252 A C A C B C B C F253 A C A C D C D C F254 A C A C D C D C F255 A C A C B C B C F256 B C A C D C B C F257 A C A C A C A C F258 A C A C B C B C F259 A C A C D C A C F260 A C A C B C A C F261 C C C C C C C C F262 C B C A C A C A F263 C C C C C C C C F264 C B C A C A C B F265 A A B A A A C A F266 A C A C A C C C F267 C A C A C A C A F268 C C C C C C C C F269 C C C C C C C C F270 C A C A C A C B F271 C A C A C A C A F272 C A C A C A C A F273 C A C A C A C B F274 A A B A A A A A F275 A A A A A A A A F276 C C C C C C C C F277 C C C C C C C C F278 C C C C C C C C F279 C C C C C C C C F280 C A C B C A C A F281 C A C B C B C B F282 A A A A A A A A F283 C A C B C A C B F284 A A A A A A A A F285 A A A B A A A A F286 A A B A A A A A F287 A A A A A A A A F288 C A C A C A C A F289 A A A A A A A A F290 C A C A C B C B F291 C A C B C A C A F292 C C C C C C C C F293 C C C C C C C C F294 C C C C C C C C *PUCCRT-Wheat Brown Rust (Puccinia triticina) *SEPTTR-Wheat Leaf Blotch (Septoria tritici) *1DP-1 Day Protectant *3DC-3 Day Curative *g/H-Grams Per Hectare *ppm-Parts Per Million

TABLE 6 Biological Activity-Disease Control in High Volume Applications (100 ppm) ALTESO* CERCBE* COLLLA* ERYSCI* ERYSGH* ERYSGT* Cmpd. No. 1DP* F20 B A A B B B F26 C A A B C B F28 B A A B A B F29 A A A A A A F30 B B A B B D F31 B A A D B B F34 B A A B B B F35 A A A A A B F36 A A A B B D F37 A A A A A B F38 A A A A A B F39 A A A A A A F78 C C A C C C F130 A A C A B C F132 A B C B B C F134 B A C B B C F138 A A A B B C F139 A A A B D C F140 A A A D B C F141 A A A B A C F154 A A A A A C F155 A A A A A C F165 A A C B B C F166 A A C A A C F169 A A C A B C F170 A A C B B C F171 A A C A B C F172 A A C A B C F173 A A C B B C F217 C C A C C C F237 B A B D B C F241 B A A D B C F242 D A A D B C F250 B B B D B C F251 B B A D D C F252 B B A D B C F253 B D A D B C F254 B B A D B C F255 B B A D B C ALTESO-Tomato Early Blight (Alternaria solani) *CERCBE-Leaf Spot of Sugar Beets (Cercospora beticola) *COLLLA-Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotricum lagenarium) *ERYSCI-Powdery Mildew of Cucumber (Erysiphe cichoracearum) *ERYSGH-Barley Powdery Mildew (Blumeria graminis f.sp. hordei; Synonym: Erysiphe graminis f.sp. hordei) *ERYSGT-Wheat Powdery Mildew (Blumeria graminis f.sp. tritici; Synonym: Erysiphe graminis f.sp. tritici) *1DP-1 Day Protectant

TABLE 7 Biological Activity -Disease Control in High Volume Applications (100 ppm) Cmpd. LEPTNO* PYRIOR* RHYNSE* UNCINE* VENTIN* No. 1DP* F20 A A A B B F26 A C C B C F28 B A A B A F29 A A C A A F30 A A C B A F31 A A C B C F34 C A C B C F35 C A C A C F36 C A C B C F37 C A C A C F38 C A C A C F39 A A A B A F78 C C C C C F130 C A A B C F132 C B B B C F134 C A A B C F138 C A A B C F139 C A A B C F140 C A A B C F141 A A A B B F154 C A A B C F155 C A B B C F165 C A A B C F166 C A A B C F169 C A A B C F170 C A A B C F171 C A A B C F172 C A A B C F173 C A A B C F217 C C C C C F237 C A D B A F241 C A B B B F242 C A D B B F250 A A B B A F251 A A B B D F252 A A A B B F253 A A B B A F254 A A A B A F255 A A A A A *LEPTNO-Wheat Glume Blotch (Leptosphaeria nodorum) *PYRIOR-Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae) *RHYNSE-Barley Scald (Rhyncosporium secalis) *UNCINE-Grape Powdery Mildew (Uncinula necator) *VENTIN-Apple Scab (Venturia inaequalis) *1DP-1 Day Protectant

TABLE 8 Biological Activity - Disease Control in High Volume Applications (25 ppm) Compound PHAKPA* Number 1DP* 3DC* F20 A A F26 A A F28 A B F29 A C F30 A B F34 A A F35 A C F36 A A F37 A C F38 A A F39 A A F44 A C F45 A A F46 A C F47 D C F59 A C F68 A C F76 A C F77 A C F78 A A F79 A C F80 A A F81 A C F95 A A F130 A B F133 A B F138 A A F139 A A F140 A A F141 A A F154 A A F155 A A F165 A B F166 A A F170 A B F172 A A F217 A C F237 A D F241 A B F242 A B F243 A B F250 B D F251 A B F252 A B F253 B D F254 A B F255 A B *PHAKPA - Asian Soybean Rust (Phakopsora pachyrhizi) *1DP—1 Day Protectant *3DC—3 Day Curative 

What is claimed:
 1. A compound of Formula I:

wherein: X is H or C(O)R₅; Y is H, C(O)R₅, or Q; Q is

R₁ is H, alkyl, alkenyl, aryl, —C(O)R₄, each substituted with 0, 1 or multiple R₄; R₂ is H, alkyl, alkenyl, aryl —C(O)R₄, each substituted with 0, 1 or multiple R₄; R₃ is H, —C(O)R₆ or —CH₂OC(O)R₆; R₄ is alkyl, alkenyl, halo, haloalkyl, alkoxy, or aryl; R₅ is alkyl, alkoxy, benzyl, benzyloxy, each substituted with 0, 1, or multiple R₇, wherein each R₇ may be substituted with 0, 1, or multiple R₄; R⁶ is alkyl or alkoxy, each substituted with 0, 1, or multiple R₄; R⁷ is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl, carbocyclic, heterocyclic, and —Si(R₄)₃, —C(O)R₄, —S(O)_(n)R₄, each substituted with 0, 1, or multiple R⁴; with the proviso that when R₁ and R₂ are H, X and Y are C(O)R₅ and R₅ is tert-butoxy.
 2. The composition according to claim 1 wherein X and Y are independently chosen from H or C(O)R₅.
 3. The composition according to claim 2 wherein X and Y are C(O)R₅ and R₅ is independently chosen from alkyl, alkoxy, benzyl, or benzyloxy, each substituted with 0, 1, or multiple R₇, wherein each R₇ may be substituted with 0, 1, or multiple R⁴.
 4. The composition according to claim 3 wherein R₁ and R₂ are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R₄, each substituted with 0, 1 or multiple R₄.
 5. The composition according to claim 4 wherein R₅ is alkoxy and R₁ and R₂ are H.
 6. The composition according to claim 5 wherein R₅ is tert-butoxy.
 7. The composition according to claim 2 wherein X and Y are hydrogen.
 8. The composition according to claim 7 wherein R₁ and R₂ are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R₄, each substituted with 0, 1 or multiple R₄.
 9. The composition according to claim 8 wherein R₁ and R₂ are independently alkyl, alkenyl, aryl, or —C(O)R₄, each substituted with 0, 1 or multiple R₄.
 10. The composition according to claim 9 wherein R₁ and R₂ are independently alkyl, or aryl, each substituted with 0, 1 or multiple R₄.
 11. The composition according to claims 8, 9, and 10 wherein the amine is protonated to give an ammonium salt of a mineral acid independently chosen from hydrogen chloride, hydrogen bromide, or hydrogen iodide.
 12. The composition according to claim 11 wherein the ammonium salt is the ammonium hydrochloride.
 13. The composition according to claim 1 wherein X is H and Y is Q.
 14. The composition according to claim 13 wherein R₁ and R₂ are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R₄, each substituted with 0, 1, or multiple R₄.
 15. The composition according to claim 14 wherein R₁ and R₂ are independently alkyl, alkenyl, aryl, or —C(O)R₄, each substituted with 0, 1, or multiple R₄.
 16. A composition for the control of a fungal pathogen including: the compound of Formula I; and a phytologically acceptable carrier material, wherein the combination of Formula I and the carrier is useful for the control of fungal and fungal like pathogens.
 17. The composition according to claim 16, wherein the fungal or fungal like pathogen is selected from the group consisting of: Mycosphaerella graminicola, Septoria tritici, Puccinia triticina Puccinia striiformis, Venturia inaequalis, Ustilago maydis, Uncinula necator, Rhynchosporium secalis, Magnaporthe grisea, Pseudoperonospora cubensis, Phakopsora pachyrhizi, Phaeosphaeria nodorum, Blumeria graminis tritici, Blumeria graminis hordei, Erysiphe cichoracearum, Glomerella lagenarium, Cercospora beticola, Alternaria solani, and Pyrenophora teres.
 18. The composition according to claim 17, wherein the fungal pathogen or fungal like pathogen is selected from the group consisting of: Septoria tritici and Puccinia tritician)
 19. A method for the control and prevention plant disease, comprising the steps of: applying a fungicidally effective amount of at least one of the compounds of Formula I to at least one surface selected from the group consisting of: at least one surface of a plant, an area adjacent to a plant, soil in contact with a plant, soil adjacent to a plant, seeds, and equipment for use in agriculture.
 20. The method of claim 19, wherein the fungicidally effective amount Formula I is applied to a surface in the range of about 0.01 g/m² to about 0.45 g/m² of Formula I. 